Virtual Photons in Magnetic Resonance FRANK ENGELKE Bruker Elektronik GmbH, Akazienweg 2, Rheinstetten 76287, Germany ABSTRACT: Magnetic resonance often relies on a semi-classical picture in which the spin particles are submitted to quantum theory and the electromagnetic field is treated as a classical field. Although in many applications there are very good reasons to work within this theoretical framework, it appears worthwhile either for educational purposes, or for studies in magnetic resonance with microscopically small samples or very weak rf fields as well as for other applications that may seem exotic today, to ask how to gain a unified view when comparing the concepts and methods of quantum electrodynamics (QED) with those of classical electrodynamics commonly used in magnetic resonance. The present article attempts to develop such a unified view for electromagnetic interactions in magnetic resonance by focusing on the concept of virtual photon exchange based on the Feynman propagator technique and by exploring the cross links between basic aspects of ‘‘semi-classical magnetic resonance’’ and the same basic aspects of magnetic resonance as seen through the frame of QED. Ó 2010 Wiley Periodicals, Inc. Concepts Magn Reson Part A 36A: 266–339, 2010. KEY WORDS: magnetic resonance; quantum electrodynamics; Feynman propagator; virtual photon; asymptotically free photon INTRODUCTION Magnetic resonance is a phenomenon that originates from the interaction between low-energy particles with spin and low-energy electromagnetic fields. In ordinary matter surrounding us, mainly liquids and solids, we usually have in mind either the electron spin or the nuclear spin, thus we speak of electron spin resonance (ESR) or nuclear magnetic resonance (NMR), respectively. A more exotic field in physics is concerned with muon spin resonance (mSR) based on the spin of the muon, a particle similar to the electron, but heavier in mass and unstable—a free muon decays in a time on the order of microseconds. Magnetic resonance techniques have found widespread applications in condensed matter physics, material science, organic and inorganic chemistry, biochemistry, molecular biology, and as an imaging technique in medical diagnostics and other fields. In these areas of concern the spin particles of interest are situated in atoms and molecules which are part of a bulk macroscopic sample. So, normally we care about manyspin systems with their manifold interactions: interactions among spin particles themselves, couplings with other physical degrees of freedom present in liquids and solids, and the response of such multispin systems to external homogeneous static fields, or pulsed or continuous-wave time-harmonic fields, or pulsed gradient fields. The various interactions Received 28 March 2010; revised 22 July 2010; accepted 29 July 2010 Correspondence to: Frank Engelke; E-mail: frank.engelke@bruker.de; Concepts in Magnetic Resonance Part A, Vol. 36A(5) 266–339 (2010) Published online in Wiley Online Library (wileyonlinelibrary.com) DOI 10.1002/cmr.a.20166 Ó 2010 Wiley Periodicals, Inc. 266 display themselves in the characteristics of magnetic resonance spectra and are the source of information that spectroscopists find valuable when studying the structures and dynamics in their samples. The spin of the electron or of an atomic nucleus is a quantum mechanical attribute. The need to switch to quantum theory to characterize spin particles in magnetic resonance appears when we talk about interactions between spins: the direct dipole–dipole coupling among nuclear spins and among electron spins, as well as between nuclear and electron spins, the coupling between electron spins and electron orbital momentum, and the coupling between nuclear spins and electron orbital momentum. Again, it is often possible to employ a qualitative classical picture as a more or less accurate approximation and as a mnemonic device to view phenomena reflected in the magnetic resonance spectra. As an example, the phenomenon of chemical shift or magnetic shielding in NMR—originating from the interaction of a given nuclear spin with the orbital momenta of surrounding electrons in a constant external field—can be understood by visualizing the moving electrons in an atom or molecule as currents that generate local magnetic fields which weakly shield the external constant field at the site of the nuclear spin, hence slightly changing its resonance frequency. As this local shielding is very sensitive to the local electron distribution around the nucleus, e.g., the chemical bonds, it provides information about the local chemical structure of the atom or molecule—hence the name for this shift of the resonance frequency: chemical shift. To explore such phenomena in greater depth and arrive at quantitative results agreeing with experimental data we have to turn to quantum theory of atoms and molecules, i.e., we use computational quantum chemistry. As it turns out for heavy elements with many electrons, one even has to take into account relativistic corrections in the quantum chemical calculations (1, 2) to explain experimental results. Quantum theory including effects that belong to the realm of special relativity leads us to relativistic quantum mechanics, which is one precursor of quantum elec- trodynamics. Another point of contact with the field of relativistic phenomena emerges when considering the interaction between the nuclear spin with the surrounding distribution of an electron being in an s state, i.e., an electron orbital state with vanishing electron orbital momentum (3). The probability for an s electron to be found at the site of a nucleus at the center of this electron orbital is different from zero. But how do we calculate the interaction energy (for electron–nucleus Coulomb interaction and electron spin-nuclear spin dipolar coupling) in the case of vanishing distance between electron and nucleus? Here, we face two problems: (a) classically for point particles and vanishing distance between them the Coulomb interaction energy diverges and (b) the point-dipole approximation that allows us to treat the spin–spin coupling as direct dipole–dipole coupling breaks down. Case (a) with energy terms diverging is a signature for relativistic effects: the interaction energy of the particles can be on the order of or may exceed the rest energy of the particles. So, at least we have to take relativistic effects into account as higher order corrections in perturbative computations. The case of the coupling between a nuclear spin and an s electron, both in the same atom, leads us to the Fermi contact interaction, a phenomenon well known in magnetic resonance. So far we have spoken briefly about quantum features of the spin-carrying particles. We have not yet mentioned quantum field theory and we have not yet addressed the subject of quantizing the electromagnetic field. Quantum electrodynamics is the quantum field theory for electromagnetic interactions and in its full extension it encompasses quantization of the electromagnetic field and the field quantization of the particles with nonzero rest mass that interact via quantized electromagnetic fields. The quantization of the electromagnetic field with particular attention for the case of magnetic resonance will be the subject of the present article. In the past, until recently, treating the electromagnetic field explicitly as a quantized field has found only relatively modest attention in the magnetic resonance literature. Instead, in the majority of the published articles electromagnetic fields are treated classically. What is the reason for treating the electromagnetic fields as classical? In magnetic resonance, we use macroscopic devices—resonators, coils, and circuits—to generate time-harmonic magnetic fields external to the spins in our sample at low frequencies, either in the radiofrequency range (meter to centimeter wavelength) or in the millimeterwave range: As a consequence, the energy of single photons is small and with state-of-the-art static-fieldgenerating cryomagnets, rf or microwave power transmitters, and circuits or resonators it is not difficult to generate either static or time-harmonic field amplitudes that formally correspond to an astronomically large number of photons. Hence, according to the argument often brought forward, electromagnetic fields can be treated classically. As we know from experimental evidence, the time-harmonic macroscopic fields have well defined field amplitudes and phases. From the quantum point of view, however, field amplitude (or equivalently, VIRTUAL PHOTONS IN MAGNETIC RESONANCE 267 Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a number of photons in a given field mode) and phase are complementary variables (4): the uncertainty of each cannot be made arbitrarily small without affecting the other; they undergo Heisenberg’s uncertainty relation. From that argument it becomes obvious that low-energy electromagnetic fields generated by macroscopic classical devices cannot be in a quantum state, which is an eigenstate of the photon number operator for a given mode or an eigenstate of the phase operator. Rigorously speaking, if the field were in a number eigenstate, the phase of the field would be entirely uncertain, and vice versa, if the field were in an eigenstate of the phase operator, the amplitude would be entirely uncertain. However, there is a class of superpositions of number states, referred to as coherent states (4, 5), where both amplitude and phase uncertainty are at a minimum simultaneously, consistent with Heisenberg’s relation, and where the relative uncertainty of both becomes negligibly small for large average photon numbers, i.e., in the classical limit, the expectation values of observables (e.g., amplitude and phase) calculated with these coherent states lead to the familiar classical equations such that, for example, the electric and magnetic fields obey Maxwell’s equations. The electromagnetic field has certain distinct and unique characteristics that warrant special attention. First, electromagnetic interactions propagate with the speed of light—hence electromagnetic fields are subject to special relativity. Even though in the 19th century Faraday, Ampere, Maxwell, Hertz, and others developed the electromagnetic theory prior to the development of the theory of special relativity by Einstein, Schwarzschild, and Lorentz at the beginning of the 20th century, and even though classical electrodynamics is thus often presented in a technical form with definitions and equations that are not form-invariant under Lorentz transformations (see Appendix A), electromagnetic fields are relativistic entities. For theoretical studies, the relativistic point of view has been taken into account by finding formulations of classical electrodynamics that satisfy form-invariance under Lorentz transformations (for the sake of brevity we say: the equations can be written in a form that is Lorentz invariant or covariant). We will use some parts of this covariant formalism throughout this article at places where it is either necessary or convenient: the covariant notation is quite compact and for certain formal chains of arguments it is a very economic one to use. When quantizing the electromagnetic field one finds photons as the elementary excitations of this field and as a consequence of the relativistic nature of the electromagnetic field one discovers that photons are entities with rest mass zero carrying a spin equal to 1 (in units of "h). Hence, photons are bosons, in contrast to spin-1/2 particles like electrons, protons, and neutrons, which are fermions. Second, if one introduces electromagnetic potentials (the well-known scalar potential f and the vector potential A), one finds that the (electric and magnetic) fields as well as Maxwell’s equations are forminvariant under gauge transformations (see Appendix B) of these potentials: the fields are gauge invariant. In classical electromagnetism one can adopt the attitude that the electromagnetic potentials are auxiliary quantities and that the ‘‘real physics’’ lies in the electric and magnetic field strengths, so one might say that gauge invariance is just a mathematical playground without physical implication. This attitude cannot be kept anymore when we turn to the quantum theoretical point of view. Here, gauge invariance in electromagnetism and invariance of the Schro¨dinger, Pauli, or Dirac equation (see Appendix E) under local phase transformations of the wave function of particles interacting with an electromagnetic field are intimately linked to each other leading, e.g., to the Aharonov-Bohm effect (6–8), which also has been verified experimentally (9). In other words, electromagnetic potentials as well as gauge transformations gain physical significance as soon as we turn to quantum theory (10). Gauge and phase invariance can be seen as a special case of geometric phases (11, 12), the latter have been investigated also by NMR (13–19). Although we will not treat these topics here, they implicitly affect our approach, for example, when choosing the proper (i.e., covariant) gauge condition for the electromagnetic field. The Dirac equation for an electron in an external, classical electromagnetic field suggests that the electron is a spin-1/2 particle (a fermion) with the gyromagnetic ratio ge ¼ ge=2me, with g as the Lande´ factor for the electron. For exactly this case, i.e., an electron with Dirac wave function c in an external electromagnetic field, where the latter is treated classically, it turns out that the Dirac theory yields exactly g ¼ 2. However, as one knows beyond doubt, for example, from high-energy electron scattering experiments, in reality g is slightly larger than 2, leading to the so-called anomalous magnetic moment of the electron (20–22). For the electron, g ¼ 2.00231930436 (22). Is there an explanation arising from a deeper quantum theory that also treats the electromagnetic field as a quantum field? The answer is affirmative and the elucidation for the electron as a fermion particle characterized by g . 2 is one of the early and certainly most impressive triumphs of quantum electrodynamics (QED) (20, 21). Because g 268 ENGELKE Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a determines the gyromagnetic ratio of the electron, it becomes clear that it establishes the Larmor frequency of an electron in an electromagnetic field, where we note that this is an electron not bound in electron orbitals of an atom or molecule, in this sense this is the g factor for a ‘‘free electron.’’ Let us turn the focus to nuclear spins. The simplest example is the proton, a spin-1/2 particle like the electron whose gyromagnetic ratio can also be written, analogous to the electron case, as gp ¼ gpe=2mp. Here, mp stands for the proton rest mass and gp denotes the proton g factor. However, it was found out experimentally that for the proton gp is quite different from 2. The reason is that although the proton possesses spin 1/2, it is, strictly spoken, not a Dirac particle, i.e., it does not obey Dirac’s equation. The fact that gp = 2 cannot be deduced from QED. The raison d’eˆtre for the proton’s defiance lies in the fact that it is a composite particle, not an elementary particle like the electron. The proton as composite is facing the external world as a stable particle and it is interacting via its electric charge and magnetic dipolar moment with electromagnetic fields. Internally, it has a quite complex structure that is governed by strong nuclear forces, which are the subject of quantum chromodynamics (QCD), not QED. Thus, to explain the origin of gp, one needs to step outside QED and treat more advanced quantum field theories like QCD (23, 24). It is also interesting to recognize that the proton, treated simply as a spinbearing particle in 1 H NMR, is still under active experimental study in the field of high-energy physics nowadays, where the goal is to learn more about the detailed origin of the proton spin from the constituents and interactions in nuclear matter (25). For the case of low energies (where ‘‘low’’ means energies small compared to the binding energy of the quarks bound together in the proton by strong, nonelectromagnetic interactions), and for energies small compared to the rest energy mpc2 of the proton, and for the purpose of exploring QED phenomena in magnetic resonance, we can treat the proton although not as a Dirac particle, but as a Dirac-like particle for which we simply have to measure the value of gp. It turns out that gp ¼ 5.585692. Therefore, in the lowenergy limit, the proton becomes very similar to the electron, in principle. Both, electron and proton are spin-1/2 particles (fermions), and their respective electric charges –e and þe, masses me and mp, and gyromagnetic factors ge ¼ ge=2me and gp ¼ gpe=2mp determine the sizes of their respective magnetic dipole moments. How can we treat nuclear spin particles different from the proton? First of all, the composite nature of the nuclei is evident. Moreover, there are nuclei like 13 C, 15 N, 29 Si that carry spin-1/2, whereas others may have spin 0 or 1 or spin 3/2 or 5/2, etc. All these spin quantum numbers mentioned here refer to the respective ground state of the nucleus—we do not consider excited nuclear states. The half-integer spin particles are fermions, while the particles with integer spin are bosons. In a quantum statistical ensemble of indistinguishable particles, the former are governed by Fermi-Dirac statistics with wave functions of the ensemble being antisymmetric under particle permutation, while the latter obey Bose-Einstein statistics, which yield symmetric wave functions. The impact of the quantum statistics on the physical behavior of spin-1/2 particle ensembles becomes noticeable in atomic or molecular electron systems governed by the Pauli exclusion principle, but also in nuclear spin systems like the dihydrogen state known as parahydrogen. In parahydrogen molecules, the two proton spins form a spin-singlet state (26–29) as opposed to orthohydrogen, where the two proton spins appear in triplet states depending on which rotational state is occupied by the two-atom molecule. The spin of a nucleus as well as its associated gn factor originate from the complex internal nuclear structure (bound protons, neutrons, which in turn are composites of quarks, undergoing strong interactions mediated by gluons). Nevertheless, in the very-low energy regime we are allowed to focus upon the electromagnetic nature of nuclei only, represented by the nucleus’ charge, its spin, and its electric quadrupole moment (the latter is zero for the proton). In the following we will not discuss nuclear-spin particles different from the proton, i.e., in the present article we focus only on low-energy QED including spin-1/2 particles like electrons and, as ‘‘nuclear spin prototypes,’’ protons. We are allowed to treat protons as Dirac-like particles with an empirical gp factor at low energies, and in such a way we can develop a formalism that treats electron spins and proton spins alike. For example, as we will see, the current density associated with the Dirac equation is easily derivable for electrons. We can take over an analogous expression of the current density for protons. The current density in general can be submitted to the Gordon decomposition (Appendix F) to extract the spin part of the current density, where the latter is needed to formulate the spin interactions in quantum electrodynamics. In the present article, we will study electromagnetic interactions with particular attention to magnetic resonance. Interaction may mean interaction between two current densities, such as a spin current density interacting with a conduction current density VIRTUAL PHOTONS IN MAGNETIC RESONANCE 269 Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a (the latter, for example, represented by the time-harmonic current in a macroscopic piece of wire). We may also say that interaction occurs between a spin particle and an external electromagnetic field, generated by a source that is not necessarily specified yet in detail and that is different from the spin particle. But taking this source of the external field as another current density, then we see that we return to the case of two interacting current densities. So, one of the central questions will be to express the electromagnetic current-to-current interaction in quantum electrodynamics. The answer to this question will directly lead us to the concept of virtual photons as a general notion in quantum electrodynamics and thus also as a vehicle for describing electromagnetic couplings in magnetic resonance. Why should we take the effort to quantize the electromagnetic field in magnetic resonance while it has been often shown that the classical description is generally sufficient? First, compared to classical and semi-classical theory, QED provides a different point of view, and comparison of the ‘‘QED language’’ with the established technical language of EPR and NMR spectroscopists could suggest alternative solutions to research questions. Furthermore, there are areas where QED might be regarded as interesting or even important, e.g., force-detected NMR microscopy and spectroscopy (30–36). For example, Butler (36) uses the Jaynes-Cummings approximation [which is often used to study the coupling between a two-level system and one mode of an electromagnetic field in quantum optics (4)] to describe a nanoscale spin resonator for force-detected NMR. Longitudinal spin relaxation induced by the resonator is studied by quantizing the mechanical oscillator and analyzing the appropriate master equation. Another field of interest is NMR spectroscopy and imaging with sub-mm or micrometer size rf coils in conjunction with samples in the volume range of picoliter to femtoliter (37–43). In these domains and dimensions one cannot take it for granted anymore that the average number of photons in an electromagnetic field mode and in a given small sample volume is astronomically large. So, the question: does the uncertainty in amplitude and phase of rf fields play a role here? Furthermore, does QED contribute when analyzing the quantum measurement process (44–47) in magnetic resonance and when exploring quantum computing and information processing using magnetic resonance (48–53), taking into account not only spin quantum states but also quantum states of the electromagnetic field? Finally, there can be a general educational benefit. For example, the QED viewpoint can provide a unified picture of electromagnetic phenomena in magnetic resonance, including the static Zeeman coupling, the coupling between spin and rf or microwave field, the coupling between nuclear spin and nearby electrons, and the dipolar coupling between two nuclear spins, to name just a few. Similarly, it is instructive to explore the limit process from quantum to classical fields, which may help us also to understand better the classical and quantum aspects of interacting spins and electromagnetic fields. Previous work illustrates the possibilities of incorporating field quantization, either of electromagnetic or other fields, in magnetic resonance. Jeener and Henin (54) investigated a general model for the coupling of an atom with an electromagnetic field in the framework of quantum optics (4), where for the simplest case of a two-level atom, expressible with pseudospin operators, parallels with NMR have been discussed. In a later article (55), the same authors provide a fully quantized theory for nuclear magnetic resonance in the framework of quasi-classical (coherent) states of the electromagnetic field. We will address some more details of Jeener’s and Henin’s work in Section ‘‘A QED NMR Probe Model: Pulsed NMR as a Scattering Process.’’ In a series of articles, Hoult et al. (56–60) have considered NMR signal reception as a near field phenomenon that can be interpreted classically via Faraday induction and quantum theoretically through virtual photon exchange, and argued against the conception of NMR as a radiative field phenomenon or a phenomenon linked to coherent spontaneous emission sometimes advocated. Boender, Vega, and de Groot (61) propose a quantum field treatment to incorporate the MAS rotor as a quantum rotor describing and characterizing rotor-frequency driven dipolar recoupling (RFDR) NMR experiments, whereas Blok (62) et al. consider relaxation processes of 67 Zn in ZnO taking into account the phonon field in the ZnO lattice including zero-point fluctuations of the phonon vacuum. Analogies between quantum optics or optical spectroscopy and magnetic resonance have been drawn (63, 64), whereas the photon picture has been extensively used in the work exploring two-photon and multi-photon transitions in EPR and NMR (65–76). Although in the majority of the aforementioned articles field quantization appears more or less as a specific tool to answer certain questions, in the present article we propose to place quantization of the electromagnetic field interacting with spin particles in the center and concentrate on the specific role of photons in such interactions. So, the focus is directed on a theoretical device that is of interest to us, which could be used as a tool. Thus, it is the 270 ENGELKE Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a manner as we look at familiar effects like Larmor precession, the nuclear spin Zeeman effect, the free induction decay, and related phenomena. It is the detailed physical background that is of interest while we derive the familiar picture of phenomena from the general view of QED. There is a variety of equivalent formalisms to choose from which can be used to represent QED, e.g., the propagator formalism, path integrals, diagrammatic techniques as an auxiliary tool, and others. In the sequel we will choose virtual photons as the central notion to describe electromagnetic couplings. The formalism or mathematical vehicle to characterize virtual photons is represented by the Feynman propagator or Feynman-Green function for the electromagnetic field, for brevity also referred to as the photon propagator. To obtain a precise idea about virtual photons as a physical concept, either in general, or in magnetic resonance, we must first lay a groundwork that includes some of the mathematics involved in generalized functions (Schwartz distributions), complex functions and functional analysis (Appendix C) as well as field operators and their commutators. To keep the main text readable, we avoid the more complex mathematical definitions and formal implications as well as the longer and tedious derivations of formal expressions. For the interested reader, these are assembled in appendices. In the section subsequent to this introduction we will provide an informal entrance and a comparison of the semi-classical view (spin as quantum object and the electromagnetic field as classical) with the view point offered by QED. In Section ‘‘The Feynman Propagator’’ we will turn to a first formal feature by deriving an expression for the photon propagator DF in general form using a development based on physical arguments introduced originally by Feynman (77). In Section ‘‘Quantization of the Electromagnetic Interaction Field: Virtual Photons’’ we will show that the photon propagator characterizes the appearance of virtual photons, whereas in Section ‘‘A QED NMR Probe Model: Pulsed NMR as a Scattering Process’’ we will link the concepts of virtual photons and asymptotically free photons with a model for pulsed NMR spectroscopy. In the subsequent sections we will use the QED view to explore phenomena intrinsic to magnetic resonance, such as Zeeman effect and Larmor precession, the interaction of a spin-1/2 particles with time-harmonic fields, a singlespin FID, and NMR radiation damping. The scope covered by the present article is by no means comprehensive, already the wealth of implications and crosslinks between full quantum descriptions with semi-classical and classical treatments is overwhelmingly large. Even if the present article covers some of the basic aspects in quantum electrodynamics, it cannot replace the study of textbooks on QED—the interested reader is referred to the literature, e.g., references (21, 22, 79–82, 85, 88–90, 92, 93, 95). In the concluding section we will summarize and tentatively show possible pathways to further explore quantum electromagnetic fields in magnetic resonance. QUANTUM ELECTRODYNAMICS IN MAGNETIC RESONANCE Before turning to technical details necessary to describe magnetic resonance phenomena by quantum electrodynamics, let us gain some informal access and overview first. We want to study low-energy particles with spin angular momentum that interact with low-energy electromagnetic fields. The latter classically obey Maxwell’s equations for the electric and magnetic vector field, or they obey d’Alembert’s wave equation for the vector and scalar potential. The interaction energy of a spin particle with magnetic dipolar momentum l situated in an electromagnetic field given by an electric field vector E and a magnetic induction field vector B is proportional to the scalar product lB, hence it depends on the relative orientation of the vectors l and B. Otherwise, the energy values lB are arbitrary and because |l| and |B| are values from a continuous set, the classical interaction energy lB is also from this set. Quantization of angular momentum leads to discrete values for the interaction energy—that means, when we choose the direction of the classical static field vector B to be the axis of quantization for the angular momentum, for spin-1/2 particles, only two discrete interaction energy values are allowed, 6g"h|B|/2. Therefore, a definite change of energy in a transition between these two energy levels can only be 6g"h|B|. What does it mean actually to quantize the electromagnetic field? To develop this idea, consider first the free electromagnetic field, i.e., a field in absence of any electric charge or current distribution. This is also a field without sources, which, again, would be charge or current distributions. The fact that such a source-free field exists at all is ensured by Maxwell’s equations or by d’Alembert’s wave equations, where in these equations all charge and current distributions are set to zero, and it can be straightforwardly shown that non-zero solutions exist to these homogeneous differential equations. We may think of free electromagnetic fields as theoretical entities insofar, that when we want to measure field quantities or we look VIRTUAL PHOTONS IN MAGNETIC RESONANCE 271 Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a at the influence of fields on charged particles, spins, etc., we always work with interacting fields. So to say, free fields are entities to be considered when the interactions are going towards zero. The energy of the classical free field is proportional to the volume integral over |E|2 þ |B|2 . If E and B here are classical vector quantities, i.e., if they are continuous functions of space and time coordinates, the energy density values are also continuous—the energy of a classical free electromagnetic field can take arbitrary values. Quantizing the electromagnetic field is synonymous with giving up the paradigm of continuity in the range of possible energy values. Instead, the possible energy values form a discrete set (Planck’s hypothesis, 1900, black-body radiation). In so far, the situation is similar or analogous (although not identical) when quantizing the angular momentum of a particle—classically there exists a continuous set of values mB, quantum-mechanically (for spin-1/2) only two discrete energy values 6g"h|B|/2 remain. Which difference do we find for the quantized electromagnetic field? When we look at a change of field energy between two discrete values of field energy, we cannot speak of a free electromagnetic field anymore. Any change of energy in the field must be compensated by some energy uptake or energy yield of particles in the field, for example the spin particle with its two allowed discrete energy values, hence these particles interact with the field. In other words, we assume energy (and momentum) conservation for the composite system field plus particle(s). Like a classical electromagnetic field, the quantized field can be submitted to Fourier decomposition and each term in the resulting Fourier series is referred to as a field mode characterized by some (angular) frequency o and wave vector k. The smallest energy change for one particular field mode is equal to "ho, with "h denoting Planck’s constant divided by 2p. When we consider the quantized electromagnetic field interacting with some spin particle placed in that field, we basically understand interaction as some discrete change of energy (and/or momentum) of the field balanced by the accompanying discrete change of energy (and/or momentum) of the spin particle: a certain number of energy quanta "ho is being exchanged. In this way, not only the admissible energy values for the field and for the particle are discretized, also the interaction itself is considered as a discrete sequence of elementary events or processes. We may consider this ‘‘sequencing’’ or even ‘‘discrete network formation’’ as one unique feature of QED, because it allows us to decompose more complex interaction scenarios occurring, for example, in multispin systems, even though it is a further question how to treat the multiparticle interactions or the interactions in bound states extended in time by analytical and perturbative schemes. We imagine the discrete sequence of interaction events as exchange processes of quanta between the interacting entities. Already early in the history of quantum theory, this quantum for the electromagnetic field has been termed photon. A photon is the smallest entity that can be exchanged in electromagnetic interaction processes. The total energy of an electromagnetic field at a given time is equal to the sum of energies arising from all photons present in the field at that time. It is to be expected that the exchange of photons is not a deterministic process. As a consequence of quantization, the quantum probabilistic character of the electromagnetic interaction has to be taken into account when we turn to QED. As we know, probabilistic behavior already appears when we describe particles like nuclei and electrons as quantum objects characterized by wave functions. Here, the classically treated electromagnetic field plays the role of an external background field and transitions between particle quantum states do not change this external field. In QED, the electromagnetic field becomes an active partner that undergoes transitions or changes of its quantum state as well when it is coupled to particles. Both, particular transitions between quantum states of particles and transitions between states of the field are related, or matched to each other. A change of the electromagnetic field state corresponds to the emission or absorption of photons, it is accompanied by a corresponding transition between particle states—in magnetic resonance these are transitions between spin states. The probabilistic nature of photon exchange as mechanism of electromagnetic interaction is characterized by uncertainty relations, either for energy, momentum, space position, or time intervals involved in the interaction (Section ‘‘Quantization of the Electromagnetic Interaction Field: Virtual Photons’’). For example, a photon once emitted is not reabsorbed necessarily with certainty. If, within a given time interval, photon absorption takes place after the photon has been emitted, we speak of a virtual photon: it constitutes an intermediate state of the electromagnetic field. If, after emission, photon reabsorption does not occur, the photon is free in the sense that for more and more extended time intervals the probability for reabsorption of that photon goes towards zero—the photon appears to be asymptotically free. Spin particles interacting with electromagnetic fields do not require any special treatment in QED. The tools developed in quantum field theory are applicable, in principle. Of course, it makes sense to 272 ENGELKE Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a take into account the specific boundary conditions under which we study magnetic resonance phenomena, like focusing on low-energy particles and fields, thus being allowed to apply nonrelativistic approximations (Section ‘‘Spin Current Density, Zeeman Hamiltonian, and Larmor precession’’). On the other side, certain tools of QED to analyze, to compare, and to illustrate electromagnetic interactions are in our hands. One of these tools that we will use in the present article is the Feynman diagrammatic technique. In Fig. 1 we have listed several Feynman diagrams to provide a correspondence between situations familiar from the semi-classical point of view of magnetic resonance and the associated QED view. Feynman diagrams are symbolic representations of rigorous mathematical expressions. Apart from that, at the same time they provide some kind of intuitive picture of the elementary interaction processes for which they stand. Without going into any details now—we will treat some of them in later sections—let us briefly discuss the basic phenomena illustrated in Fig. 1. The first one, [Fig. 1(A)], represents the interaction of a spin-1/2 particle with an external electromagnetic field. The source of the field might be unspecified or it might be explicitly given (e.g., a current in a coil). In the corresponding Feynman diagram, for example the diagram (a) in Fig. 1(A), we draw a line with an arrow to represent the spin particle. This directed line enters a vertex, where the discrete ‘‘interaction event’’ occurs, here it is the emission or absorption of a virtual photon, symbolized by a wavy line. After the interaction event the spin particle is left in a state (drawn by an outgoing line with arrow) different from the initial state. Virtual photon exchange happens between the spin particle and the (nonspecified) external source of the electromagnetic field. We may add more details to this process by explicitly specifying the external source current [diagram (b)]. In that case, the virtual photon exchange affects both interaction partners, the current density that corresponds to the spin particle (Section ‘‘Spin Current Density, Zeeman Hamiltonian, and Larmor Precession’’) and the current density that represents the external source. The two diagrams (a and b) provide the basis to appreciate the concept of the ‘‘single-spin free induction decay’’ and the basic mechanism of NMR radiation damping, both treated in Section ‘‘Single-Spin FID and NMR Radiation Damping’’ Figure 1(B) offers a glance to more details when a spin particle interacts with an rf field, for example, during the application of an rf pulse. Classically, the rf current in a coil or circuit generates an electromagnetic field that interacts with the spin inside or nearby the coil. We call this field the near field, characterized by a distance to the source (the current in the coil wire) small compared to one wavelength. A free standing coil (that means a coil not completely surrounded by a shield) also generates an rf field at larger distances (one wavelength and more) which is the far field. In Fig. 1(B) in the center, the graphical plot on top shows a snapshot of the rf far field magnitude |B| generated by an rf current in a solenoidal coil (6 turns, pitch angle x, limit radius r0, cf. Ref. 87) located in the center of the field distribution. Taking the center part of that field distribution (field of view magnified by a factor of 5), we see the near field close to the coil. Under the QED point of view, we may interpret the interaction between spin and near field as virtual photon exchange while the far field arises from those photons that, for example, are emitted by the rf current and that are not absorbed within a given time interval, thus they are asymptotically free photons. This principal situation is shown by the Feynman diagram in Fig. 1(B), more details will be treated in Sections ‘‘A QED NMR Probe Model: Pulsed NMR as a Scattering Process’’ and ‘‘Interaction of a Spin-1/2 Particle with External Time-Harmonic Fields.’’ Likewise, direct dipole– dipole interaction, a specific example for a spin–spin interaction illustrated in Fig. 1(C) can be understood as virtual photon exchange. Finally, even spin-lattice relaxation (characterized by the time constant T1) can be cast into the QED language, Fig. 1(D). Every transition of a spin between Zeeman levels corresponds to a virtual photon exchange between the spin particle and the lattice-degrees of freedom, where the lattice represents a partner for the interaction with a stochastic or statistically fluctuating current density, resulting from the stochastic motion, e.g., of molecules in a liquid. In a similar way, spin–spin relaxation could be treated. In the present article we focus on the basic interactions exemplified in Fig. 1(A,B), i.e., we deal with the interaction of a single spin (or more than one, but then isolated spins) with the static field and with an rf field or microwave field and we provide a QED explanation of the electromotive force induced in a coil or circuit by a single spin. We will call that ‘‘single-spin FID,’’ although an FID of a macroscopic sample contains more features, for example, the dephasing of magnetization originating from many spins with slight resonance offsets, spin–spin relaxation, explicit spin–spin couplings, etc. These latter phenomena are not treated in the present article. On the other hand, NMR radiation damping—to be understood as the back action of the rf current generated by the electromagnetic field originating from the spin particle—also appears when only one spin is VIRTUAL PHOTONS IN MAGNETIC RESONANCE 273 Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a Figure 1 Basic interaction processes occurring in magnetic resonance. The middle column shows in a schematic way (A) a single spin interacting with an external classical field, (B) the near field and the far field generated by an rf coil, (C) spin dipole-dipole interaction, and (D) a level diagram associated with spin-lattice relaxation. The diagrams in the right column represent Feynman diagrams for the corresponding QED elementary processes. 274 ENGELKE Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a present. Admittedly, this effect is extremely small and ‘‘hard to measure’’ for a single spin. So, the scope of the present article might be summarized as treating the basic and elementary interaction processes relevant for magnetic resonance, like virtual photon exchange and emission of asymptotically free photons. These elementary processes could be used as building blocks to deal with more complex situations in bulk samples including multi-spin systems characterized by interactions between like spins and unlike spins, spin–lattice relaxation, and spin–spin relaxation. To finally achieve the proximity to magnetic resonance phenomena in the form as we know it from the NMR and ESR spectroscopy literature, we meet approximations and assumptions: first, we start with the simple classical expression of Coulomb interaction energy and generalize this step by step to arrive at a covariant expression for the Feynman propagator. After analyzing it and deriving the associated concepts of virtual photons and asymptotically free photons (Sections ‘‘The Feynman Propagator’’ and ‘‘Quantization of the Electromagnetic Interaction Field: Virtual Photons’’) we introduce a photon scattering model for pulsed NMR (Section ‘‘A QED NMR Probe Model: Pulsed NMR as a Scattering Process’’). Here, we treat the current densities as nonoperator quantities, which is allowed when we would treat the spin particles either as classical or when we treat them as quantum objects, in the latter case in first quantization (with the wave function as a function). For the spin particles we perform the transition to the nonrelativistic realm (slow velocities, low energies, and low momenta). Thus three cornerstone assumptions are involved: (a) the electromagnetic field is assumed to be a relativistic quantity (expressed by the associated Feynman propagator), (b) initially the spin current density is introduced as a covariant quantity, however, for the spin particles we apply the nonrelativistic approximation (i.e., small velocities, small energies, and small momenta), see Sections ‘‘A QED NMR Probe Model: Pulsed NMR as a Scattering Process’’ and ‘‘Spin Current Density, Zeeman Hamiltonian, and Larmor Precession,’’ and finally (c) we consider the spin particles as quantum objects (with a spatial and spin wave function) with the result that the spin current density is also a function (no second quantization of the fermion field). We start with (a) in deriving the Feynman propagator. THE FEYNMAN PROPAGATOR As indicated in the introduction, we must create some formal basis to fully appreciate the concept of virtual photons. For edifying reasons let us begin with an almost tautological definition of the term interaction. Two partners (particles, fields, etc.) are interacting with each other when partner 1 acts upon partner 2 and partner 2 also acts upon partner 1. So, we may explain interaction by reducing it to the concept of action. In physics, the quantity of action is defined as the time integral over the Lagrange function L. In classical mechanics, the Lagrange function is given by the difference of kinetic and potential energy of particles. The potential energy term constitutes the interaction of the particle with either an external field or with an interaction partner. If for the moment we disregard kinetic energy and turn to field theory, the Lagrange function for the interaction becomes (up to a sign) equal to the interaction Hamiltonian or interaction energy. Therefore, we will start our discourse by discussing a stepwise generalization of formal expressions for the electromagnetic interaction energy and then turn to the quantity of action associated with it. We begin by considering two point charges Q1 and Q2 at distance r. The electrostatic interaction energy reads EQ ¼ 1 4pe0 Q1Q2 r [1] where e0 denotes the dielectric permittivity of the vacuum and r is equal to the distance between the two charges Q1 and Q2. The Coulomb interaction energy EQ can take positive or negative values, depending on the signs of Q1 and Q2, where for opposite charges, i.e., attractive forces, we get EQ , 0. We make a first step towards generalization by not assuming point charges, but electric charge densities r1(x) and r2(y) distributed in space given by the position vectors x and y with r ¼ |x À y|. Thus, EQ ¼ 1 4pe0 Z d3 x Z d3 y r1ðxÞr2ðyÞ r [2] where now two integrals appear over the threedimensional volumes with volume elements d3 x and d3 y occupied by elements of the charge densities r1(x) and r2(y), respectively. A similar expression can be written down for the interaction energy of two electromagnetic currents or current densities j1(x) and j2(x): EC ¼ À m0 4p Z d3 x Z d3 y j1ðxÞj2ðyÞ r [3] with m0 being equal to the magnetic permeability of the vacuum. We may also admit charge and current VIRTUAL PHOTONS IN MAGNETIC RESONANCE 275 Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a densities that explicitly depend on time and, for generality, we may assume that charge distributions as well as current distributions are present simultaneously. The total interaction energy reads EI ¼ 1 4p Z d3 x Z d3 y 1 e0 r1ðx;tÞr2ðy;tÞÀm0j1ðx;tÞj2ðy;tÞ r ¼ m0 4p Z d3 x Z d3 y c2 r1ðx;tÞr2ðy;tÞÀj1ðx;tÞj2ðy;tÞ r [4] where c2 ¼ 1/e0m0. Let us introduce the four-position vector xm ¼ (ct,x) including time and space coordinates, where the superscript m counts the components, with m ¼ 0 for the time coordinate (multiplied by the speed of light c), x0 ¼ ct and m ¼ 1, 2, 3 referring to the three spatial components of the vector x. Likewise, let us merge the scalar charge density r(x) and the vector current density j(x) into a single four-vector jm ¼ (rc,j) and refer to it as the four-current density. For more details on the definition of four-vectors in Minkowski space-time, we refer to Appendix A. In Eq. [4], let us drop the subscripts 1 and 2 labeling the charge and density distributions because we recognize that the space-time coordinates x and y distinguish them already. So, Eq. [4] appears in the concise form EI ¼ m0 4p Z d3 x Z d3 y jm ðxÞjmðyÞ r [5] with the scalar product, jm ðxÞjmðyÞ¼j0 ðxÞj0ðyÞ ÀjðxÞjðyÞ, in Minkowski space-time. Note, in expressions like am bm we apply the sum convention: am bm : a0 b0 þ (a1 b1 þ a2 b2 þ a3 b3) (see Appendix A). We recognize that until now we have made no explicit assumptions about how fast the interaction may propagate between jm (x) and jm(y)—in fact, in Eq. [5] we implicitly assumed that the interaction propagates infinitely fast. This becomes more obvious if we rewrite Eq. [5] as EI ¼ m0 4p Z d3 x Z d3 y Z dy0 jm ðxÞdðx0 À y0 ÞjmðyÞ r [6] where we have inserted Dirac’s d function with the time difference x0 À y0 as an argument and an additional integral over the time coordinate y0 . Integrating the whole expression in [6] over dy0 along the entire time axis, we come back to Eq. [5]. Alternatively, we could have performed the time integral also over dx0 instead of dy0 , with the same result. In other words, the time coordinates appearing in jm (x) and in jm(y) are equal, x0 ¼ y0 , as dictated by the d function—the interaction occurs instantaneously. As stated earlier, the Lagrange function L for the interaction equals the interaction Hamiltonian or interaction energy EI up to a sign, i.e., we have L ¼ ÀEI. Furthermore, the time integral over L is equal to the action functional W1 for the interaction considered: W1 ¼ Z dx0 c L ¼ À 1 c Z dx0 EI ¼ À m0 4pc Z dx0 Z d3 x  Z d3 y Z dy0 jm ðxÞdðx0 À y0 ÞjmðyÞ r ½7Š A few words to explain what is meant by action functional. A functional is a mapping that assigns a number to a function or to a vector of functions (likewise, a function assigns numbers to numbers or to a vector of numbers). In the case of the action functional [7], we have the function jm (x)d(x0 Ày0 ) jm(y)/r. Integrating over the full range of all the variables (i.e., entire time dimension and entire space) assigns a number, W1 to the vector of two functions j(x) and j(y). Now from Eq. [7] on we are not concerned with interaction energy anymore, but more generally with the action related to the interaction. The integrals over the time intervals dx0 and the three-dimensional volume elements d3 x can be formally assembled together as one integral over the space-time element d4 x. Likewise, the same can be achieved for the time intervals dy0 and volume elements d3 y to obtain d4 y. Hence, the action functional [7] can be written with two space-time integrals as: W1 ¼ À m0 4pc Z d4 x Z d4 y jm ðxÞdðx0 À y0 ÞjmðyÞ r [8] Now we introduce, for physical reasons, the requirement that any action from jm (x) to jm(y), or vice versa (thus, interaction), can only be a retarded action, i.e., it takes a certain time to propagate from one region in ordinary space to another one at distance r. When this propagation occurs with the speed of light, c, the time interval for propagation is equal to r/c. We can easily modify Eq. [8] to take into account retardation by modifying the argument of the d function accordingly: W1 ¼ À m0 4pc Z d4 x Z d4 y jm ðxÞdððx0 À y0 Þ À rÞjmðyÞ r [9] With Eq. [9] we have obtained a first remarkable result. To see this, let us define the function 276 ENGELKE Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a Dretðx À yÞ ¼ À m0 4pc dððx0 À y0 Þ À rÞ r ; r ¼ jx À yj [10] such that the action W1 can be written as W1 ¼ Z d4 x Z d4 yjm ðxÞDretðx À yÞjmðyÞ ¼ Z d4 xjm ðxÞAR mðxÞ and where we have implemented the retarded potential AR m(x) generated by the current jm(y), AR mðxÞ ¼ Z d4 yDretðx À yÞjmðyÞ ¼ À Z d3 y Z dy0 m0 4pc dððx0 À y0 Þ À rÞ r jmðyÞ ¼ À m0 4pc Z d3 y jmðx0 À r; yÞ r ½11Š as the convolution integral of Dret( xÀ y) with the current density jm(y). The kernel of the first integral in Eq. [11], Dret(x À y), is referred to as the retarded Green function associated with the inhomogeneous wave equation. It is also called the retarded propagator (see Appendix B). After having introduced retarded action, returning to Eq. [9], let us perform the next step: we consider the time ordering of events. In Eq. [9] we have done so already in an implicit way by expressing retardation through the d function with the argument (x0 Ày0 )Àr. Because r is strictly positive, the integrals in [9] are nonzero if and only if x0 Ày0 . 0, which means x0 . y0 : the event at time instant y0 (for example, a change of the current density element located in space position y) is earlier than the event at time x0 (when the field change caused by the previous current density change arrives at the current density element in space position x)—the cause precedes its action. In general, when we talk about interaction, we have to admit that, in principle, also the inverse time order may happen in conjunction with an exchange of the two positions in space, i.e., an event at position x happens first at time x0 , the field change travels to position y where it arrives at a later time y0 such that, as causality dictates again, we have x0 , y0 . Since both event orders are allowed, the total action is given as the arithmetically weighted sum of both: W ¼ W1 þ W2 2 ¼ À m0 4pc Z d4 x Z d4 y  jm ðxÞ½dððx0 À y0 Þ À rÞ þ dðÀðx0 À y0 Þ À rފjmðyÞ 2r [12] The first d function on the right-hand side of Eq. [12] stands for the time order x0 Ày0 . 0, while the second one takes the reverse order into account, x0 Ày0 , 0. The fact that both time orders must appear is almost trivial for an interaction. j(y) acts on j(x), so x0 Ày0 . 0 as well as j(x) acts on j(y), hence we have x0 Ày0 , 0. We may depict this diagrammatically as shown in Fig. 2. The two interacting current densities are drawn as lines with arrows, the interaction between them as a wavy line. In the diagrams the time axis points into vertical upward direction and Figs. 2(A,B) correspond to the two time orderings as explained above. In Fig. 2, we have drawn second-order Feynman diagrams symbolizing the elementary electromagnetic interaction process occurring between two electromagnetic current densities. A systematic introduction into general Feynman diagrammatic techniques can be found, for example, in references (81, 89, 90, 124). We observe that the d function is even, i.e., it holds dðÀðx0 À y0 Þ À rÞ ¼ dððx0 À y0 Þ þ rÞ [13] such that Eq. [12] formally appears to be the sum of a time-retarded and a time-advanced part. As we have discussed above, the latter just reflects the alternative time ordering (which always takes place together with an exchange of spatial coordinates) that we have to admit in interaction processes. The timeadvanced part does not indicate a violation of causality nor does it describe noncausal evolution backwards in time, although formally, sometimes in the literature, it is termed anticausal. So, the action functional for the electromagnetic interaction of two current densities reads Figure 2 Diagrammatic representation of the interaction between two currents, (A) where j(y) acts on j(x) and (B) vice versa, j(x) acts on j(y), representing two opposite time orderings. The current densities are drawn as lines with arrows, the electromagnetic interaction between them as wavy lines. The diagrams shown represent two examples of second-order Feynman diagrams. VIRTUAL PHOTONS IN MAGNETIC RESONANCE 277 Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a W ¼ W1 þ W2 2 ¼ À m0 4pc Z d4 x Z d4 y  jm ðxÞ½dððx0 À y0 Þ À rÞ þ dððx0 À y0 Þ þ rފjmðyÞ 2r [14] The difference between Eqs. [9] and [14] is that in Eq. [9] only one fixed time order is taken into account, while Eq. [14] is more general, because it also allows the reverse order when simultaneously the space coordinates are reversed. Both time orders correspond to retarded action. From now on, for the sake of simplicity in notation, we adopt Heaviside-Lorentz units (which are characterized by setting e0 ¼ 1 and m0 ¼ 1) and, in addition, we also set c ¼ 1, "h ¼ 1. In the resulting system of physical units it then appears that energy, mass, linear momentum, wave number, and frequency have the same unit: 1/meter. The corresponding units in SI are obtained by multiplying accordingly with c and/or "h, the SI units for the field quantities by re-introducing e0 and m0 accordingly (78). We take a look at the formal Fourier decomposition of the d function, dðx0 Þ ¼ 1 2p Zþ1 À1 expðÀiox0 Þdo; [15] which tells us that, upon integration, it contains positive as well as negative frequencies o. As it will turn out, for the case of the quantized electromagnetic field these frequencies o correspond to energies "ho for photons. Again for physical reasons, anticipating the photon picture that we will adopt when we turn to QED, we require that o is strictly positive or zero, not negative. This is equivalent to admitting only positive (or zero) energy values carried by a single photon. To take this requirement into account, we have to restrict the integration range in Eq. [15] to run over o values only from 0 to 1 instead of the full range of À1 to 1 such that we arrive at the modified d function defined by the ‘‘half-sided’’ Fourier integral (note here, by definition, the different pre-factor 1/4p2 ). dþðx0 Þ ¼ 1 4p2 Zþ1 0 expðÀiox0 Þdo [16] We will investigate the detailed properties of dþ later in Section ‘‘Quantization of the Electromagnetic Interaction Field: Virtual Photons’’ (see also Appendix C). For the moment it may suffice to say that the features of dþ are central to the mathematical description of photons appearing in interaction processes. One remark in advance: while Dirac’s d function can be considered as a real-valued generalized function, i.e., its arguments are on the real line and the values of d are, loosely speaking, either zero or infinite, but real-valued, this ‘‘real-valuedness’’ is not the case anymore for dþ. So, the requirement of positivity for the photon energy with the consequence of the restricted integration range in Eq. [16] leads to a phenomenon called time dispersion: dþ becomes complex-valued (with a real and an imaginary part). To understand the consequences, let us rapidly anticipate some of the steps that lead into QED, more thoroughly discussed in later sections. The positivity requirement for the energy of photons, exchanged between the current densities, has far-reaching implications. First, the quantity of action, W, becomes a complex-valued quantity. Second, with the probability amplitude Z in QED (22) defined as: Z ¼ expðiWÞ [17] for the photon propagation in QED, the resulting probability for a photon propagating from one current to the other current is equal to |Z|2 . Thus if W is real, we get |Z|2 ¼ 1 and if W appears to have an imaginary part, we see that |Z|2 , 1. The latter statement means that not every photon emission leads necessarily to photon re-absorption—there is a finite probability that photons ‘‘break free.’’ We will discuss that in more detail in Sections ‘‘Quantization of the Electromagnetic Interaction Field: Virtual Photons’’ and ‘‘A QED NMR Probe Model: Pulsed NMR as a Scattering Process.’’ So, if we modify Eq. [14] by replacing d by dþ, we arrive at W ¼ À2p 1 4p Z d4 x Z d4 y  jm ðxÞ½dþððx0 À y0 Þ À rÞ þ dþððx0 À y0 Þ þ rފjmðyÞ 2r where the additional factor 2p in front of the two spacetime integrals takes into account the different prefactor in Eq. [16] as compared to the pre-factor in Eq. [15]. The following identities hold (see Appendix C) dððx0 À y0 Þ À rÞ þ dððx0 À y0 Þ þ rÞ 2r ¼ dððx0 À y0 Þ2 À r2 Þ ¼ dððx À yÞ2 Þ dþððx0 À y0 Þ À rÞ þ dþððx0 À y0 Þ þ rÞ 2r ¼ dþððx0 À y0 Þ2 À r2 Þ ¼ dþððx À yÞ2 Þ ½18Š 278 ENGELKE Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a where (xÀy)2 is equal to the squared four-distance between the two space-time points of the elementary interaction events, i.e., ðx À yÞ2 ¼ ðx0 À y0 Þ À jx À yj2 ¼ ðx0 À y0 Þ À r2 . When introducing [18], the expression for the electromagnetic action functional reads W ¼ À 1 2 Z d4 x Z d4 yjm ðxÞdþððx À yÞ2 ÞjmðyÞ [19] Let us introduce Dmn F ðxÞ ¼ Àgmn dþðx2 Þ; [20] where gmn designates the metric tensor (cf. Appendix A) and refer to DF as Feynman propagator or Feynman-Green function for the electromagnetic interaction. Similar to the retarded propagator Dret defined by Eq. [10], the Feynman propagator DF is a further Green function associated with the wave equation (Appendix B). With the definition [20], the action functional [19] can be written as W ¼ 1 2 Z d4 x Z d4 yjnðxÞDmn F ðx À yÞjmðyÞ: [21] The expression [21] states that the electromagnetic action (interaction) between two current densities jn(x) and jm(y) is mediated by the Feynman propagator DF(xÀy) for the electromagnetic field. We remark that [21] is quite general, however, it can be specialized for the case of spin–spin interactions as well as for interactions between spins and resonator, by specifying the current densities accordingly. There is no principal restriction for the current density: it can represent a spin current density or a current density due to electron conductivity, microscopic or macroscopic. We will turn to that subject in more detail in Section ‘‘Spin Current Density, Zeeman Hamiltonian, and Larmor Precession.’’ In analogy to the retarded potential, Eq. [11], the integral over d4 y is equal to the four-potential An (x) at spacetime point or region x generated by the current density jm(y) at space-time point or region y, An ðxÞ ¼ Z d4 yDmn F ðx À yÞjmðyÞ: [22] Hence, W ¼ 1 2 Z d4 xjnðxÞAn ðxÞ [23] In summary, we have started our discussion with the classical expression for the interaction energy for two interacting current densities and introduced (a) time retardation, (b) time ordering of events, and (c) positivity of the energy exchanged as a quantum between the interaction partners. As a result we obtain the Feynman propagator DF for the electromagnetic field. So far, we are still (almost) within the scope of classical electrodynamics including special relativity (retarded field propagation with finite speed). We have not yet properly quantized the electromagnetic field. In doing so, in the next section, we will find an interpretation for DF in physical terms. The general result [21] remains valid in a quantized field theory. Focusing on magnetic resonance, it becomes necessary to specify the general current densities jm for spins and/or electric currents. We will accomplish that in Section ‘‘Spin Current Density, Zeeman Hamiltonian, and Larmor Precession.’’ QUANTIZATION OF THE ELECTROMAGNETIC INTERACTION FIELD: VIRTUAL PHOTONS Quantization of the electromagnetic field involves two formal ingredients. First (a) the field functions Am (x), i.e., the four-vector potential Am ðxÞ ¼ ðA0 ðxÞ; AðxÞÞ including the scalar potential A0 (x) ¼ f/c and the vector potential A(x), become field operators. Furthermore (b), generally, these field operators are subject to certain commutation or anticommutation relations that determine the basic nature of the quantum field. This procedure related to these two cornerstones (a) and (b) is called canonical quantization and will be the basis for our attempt to discover virtual photons in magnetic resonance. From a practical point of view it is advantageous to begin with the classical Fourier expansion of the field functions (four-potentials) in three-dimensional momentum space (k space), reading AmðxÞ ¼ Z d3 k ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 2pð Þ3 2ok q X3 l¼0 eðlÞ m ðkÞ Â aðlÞ ðkÞeÀikx þ aðlÞþ ðkÞeikx   ½24Š Here k ¼ km ¼ ðk0 ; kÞ denotes the contravariant four-momentum vector (see Appendix A) with k0 proportional to the energy variable "hck0 of the field mode k and k equal to the usual wave number vector such that "hk is equal to the three-momentum. In space-time there are generally four different polarization vectors e ðlÞ m ðkÞ ¼ ðe ðlÞ 0 ðkÞ; ÀeðlÞ ðkÞÞ, enumerated by the superscript l ¼ 0, 1, 2, 3. The Fourier coefficient a(l) (k) and its conjugate complex a(l)þ (k) are functions of the three-momentum k. VIRTUAL PHOTONS IN MAGNETIC RESONANCE 279 Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a The exponentials exp(6ikx) contain the four-scalar product kx ¼ km xm ¼ ðk0 ; kÞðx0; ÀxÞT ¼ k0 x0 À k Á x: Summation over all polarization directions and integration over k-space yields the four-vector Am (x) as a function of space coordinate vector x and time coordinate x0 . Converting the field functions Am (x) into operators leads us to ask which of the constituents in the integral expression [24] takes over the operator role. This role is filled by the Fourier coefficients a(l) (k) and a(l)þ (k), that are required to satisfy the following canonical commutation relationships (CCR): ½aðlÞ ðkÞ;aðrÞþ ðk0 ފ ¼ Àglr d3 ðk À k0 Þ; l;r ¼ 0;1;2;3 [25] with all other combinations of elements in the commutator brackets different from those in [25] yielding zero. Thus, with [24] being read as a Fourier expansion of field operators and with the Fourier coefficients required to satisfy the CCR [25], we have performed the formal task of quantizing the electromagnetic field. This allows us to calculate commutators of field operators, [Am (x), An (y)], or products of field operators Am (x)An (y), etc. We may define the Lagrangian density for the free or the interacting electromagnetic field and obtain the associated Hamiltonian (79–82), which for the free field turns out to be identical in form with the Hamiltonian for a system of harmonic oscillators. As explained in texts on quantum field theory and quantum electrodynamics, the operators a(l) (k) and a(l)þ (k) reveal themselves as annihilation and creation operators for photons, the quanta of the electromagnetic field. Suppose there is a state |0i of the electromagnetic field with no photons present in the field, also called the ground state or the vacuum state of the field and define aðlÞ ðkÞj0i ¼ 0; aðlÞþ ðkÞj0i ¼ j1i [26] where |1i denotes a state of the field with exactly one photon present with momentum k and polarization e(l) (k). We may generalize this for n photons, aðlÞ ðkÞjni ¼ ffiffiffi n p jn À 1i; aðlÞþ ðkÞjni ¼ ffiffiffiffiffiffiffiffiffiffiffi n þ 1 p jn þ 1i ½27Š Applying a(l) (k) and subsequently a(l)þ (k) to the field state |ni we obtain from [27]: aðlÞþ ðkÞaðlÞ ðkÞjni ¼ njni [28] which qualifies the product operator a(l)þ (k)a(l) (k) as the photon number operator. The field states |ni with a precisely defined number n of photons in a given mode (l, k) are eigenstates of the photon number operator and are called Fock states. These form an orthonormal basis set of states in a state space called Fock space, a specific example of an infinitedimensional Hilbert space. We mentioned the Fock states in the introduction when discussing the uncertainty relation of field amplitude and phase and we maintained already that Fock states cannot correspond to states of the electromagnetic field in the classical limit. In quantum field theory it makes a difference whether we say that the field contains zero photons, i.e., it is in its vacuum state |0i, or we say that there is no field. In the latter case, there is nothing to talk about, in the former case, there is quite a bit to discuss. We may calculate expectation values of operators with field states to be compared with measurements, so for example we might be interested in vacuum expectation values. Interestingly, we find for instance, h0jAm ðxÞj0i ¼ 0; h0jAm ðxÞAn ðyÞj0i 6¼ 0; [29] which can be easily verified when taking into account Eqs. [24–26]. While the vacuum expectation value of the field operators vanishes [likewise this is also true for the vacuum expectation values of the electric field and the magnetic induction field calculated from Am (x)], it is not the case for the vacuum expectation value of higher order products. Thus, the variance, or two-point correlation, or fluctuation amplitude of field quantities can be nonzero in the vacuum state— a typical situation occurring in quantum field theory. We return to the discussion we began in the previous section concerning the two current densities interacting with each other, i.e., the current density jn (x) generating the field An (y) at the space-time position y of the current density jm (y) and vice versa, the current density jm (y) producing the field Am (x) at the space-time position x of the current density jn (x). The interaction of the two current densities has been expressed by Eq. [21]. But consider the following: instead of correlating the two current densities in that way, we can also correlate the two associated fields by forming the product Am (x)An (y) and calculating expectation values for given field states—the simplest and most straightforward would be the vacuum expectation value. Moreover, because we saw in the previous section that time ordering is essential in 280 ENGELKE Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a describing interactions to ensure causal behavior, we may include that in our field correlation and calculate not just h0|Am(x)An(y) |0i, but calculate the time-ordered vacuum expectation value h0|T(Am (x)An (y)) |0i, where Dyson’s time ordering operator T has been introduced, defined as TðAm ðxÞAn ðyÞÞ ¼ Am ðxÞAn ðyÞ; x0 > y0 An ðyÞAm ðxÞ; y0 > x0 & ¼ yðx0 À y0ÞAm ðxÞAn ðyÞ þ yðy0 À x0ÞAn ðyÞAm ðxÞ [30] y denotes the Heaviside step function defined as y(x0 Ày0 ) ¼ 1 for x0 Ày0 . 0 and zero otherwise. We have now all the means available to calculate h0|T(Am(x)An(y)) |0i. As shown in detail in Appendix C, this calculation yields h0jTðAm ðxÞAn ðyÞÞj0i ¼ ÀiDmn F ðx À yÞ ¼ igmn dþððx À yÞ2 Þ ½31Š Thus, we find that for a quantized electromagnetic interaction field the Feynman propagator equals (up to a constant prefactor) the vacuum expectation value of the time-ordered field operator product Am (x)An (y), that is, the Feynman propagator corresponds to the two-point vacuum field correlation function. Note, the correlation here includes time and space correlation—we are in space-time. Reading the expression [31] as a space-time twopoint correlation function opens up the possibility of an even more extended interpretation of the Feynman propagator DF. First, we observe that when we insert the expansion [24] for the field operators into the expression for the vacuum expectation value of the time-ordered field operator product, h0jTðAm ðxÞAn ðyÞÞÞj0i, terms like h0jTðaðlÞ ðkÞeÀikx þ aðlÞþ ðkÞeikx ÞðaðlÞ ðkÞeÀiky þ aðlÞþ ðkÞeÀiky Þj0i ¼ ¼ h0jTaðlÞ ðkÞeÀikðxÀyÞ aðlÞþ ðkÞj0i ½32Š appear. The last line in [32] may be read from right to left as follows: initially there is the photon vacuum |0i. The creation operator a(l)þ (k) creates the singlephoton state j1 >¼ aðlÞþ ðkÞj0i. As indicated by the time ordering and the exponential function eÀik(xÀy) , the photon propagates (assuming y0 , x0) from y to x. At space-time point x the annihilation operator a(l) (k) annihilates the single-photon state again, which leaves the field in the vacuum state: j0i ¼ aðlÞ ðkÞj1i. The process of creating a photon in y, letting it propagate to x, then annihilating that photon in x, appears in a time-ordered fashion—i.e., the photon is first created at time y0 , and then later at time x0 it is annihilated (left side of Fig. 3)—formally this is taken care of by the time-ordering operator T. For the case x0 , y0 (right diagram in Fig. 3) the photon is created in x, propagates to y where it is annihilated again. The photon only exists while propagating from y to x (or from x to y when the time order is reversed), the initial and final field states are photon vacuum states. It is for that reason that the intermediate single-photon state, j1i ¼ aðlÞþ ðkÞj0i, appearing here is referred to as occupied with a virtual photon. Virtual photons emerge as intermediate states between the initial and final photon vacuum state. Therefore, the Feynman propagator, also referred to as the photon propagator, represents the mathematical vehicle describing virtual photons. With Eq. [31] we could set up a new expression for the action functional W, Eq. [21], which now has also a new interpretation for the probability amplitude Z ¼ exp(iW), Eq. [17], that governs the probability |Z|2 for the photon propagation between the site of emission and the site of absorption. Photons are being exchanged with probability |Z|2 1. Photon propagation is thus not a deterministic process, it exhibits some uncertainty measure expressed by |Z|2 admitting the possibility that an actual photon exchange happens, as illustrated in Fig. 3, emission and subsequent reabsorption (the appearance of a virtual photon) as well as admitting the possibility that photons emitted are not Figure 3 Pictorial representation of the photon propagator with explicit time ordering according to Eq. [30]. For x0 , y0 the photon is created in space-time point x and propagates to space-time point y where it is annihilated (right diagram). For y0 , x0 the photon is created in y and propagates to x where it is annihilated (left diagram). VIRTUAL PHOTONS IN MAGNETIC RESONANCE 281 Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a reabsorbed or photons absorbed have not been emitted in the past. In the scheme drawn here it seems that the virtual photon apparently emerges out of nothing and disappears into nothingness. This is, of course, not the case, we just have isolated the interaction part— interaction occurs between two current densities jm (x) and jn (y) and the diagrams in Fig. 3 can be seen as subdiagrams contained in the diagrams of Fig. 2. So, it is more appropriate to say that virtual photons are emitted by one current density and reabsorbed by another (or the same) current density. Emission of virtual photons changes the state of the particles that constitute the current density, likewise the reabsorption of virtual photons. In Fig. 2 we have indicated that by a kink in the lines symbolizing the current densities, appearing when emission or absorption occurs. The particles that compose the current densities in Eq. [20] might be conduction electrons in a piece of metal wire being a part of a coil, or it might be a spin particle in a specific spin state. The photon propagator governs the electromagnetic interaction between current densities. To see this, we must turn back to Eqs. [20] and [31] and further analyze the distribution dþððx À yÞ2 Þ, an essential constituent of the Feynman propagator DF(xÀy) and arising from Eq. [31]. As shown in lengthy detail in Appendix C (see, Eqs. [C8] to [C17]), DF(xÀy) turns out to be, Dmn F ðx À yÞ ¼ Àgmn dþððx À yÞ2 Þ ¼ À gmn 4p2 pdððx À yÞ2 Þ À i} 1 ðx À yÞ2 !" # ½33Š As already mentioned in Section ‘‘The Feynman Propagator’’ when introducing the probability amplitude Z (Eq. [17]), we observe in Eq. [33] that DF(x À y) is complex-valued; it consists of a real part, given by Dirac’s d distribution, and of an imaginary part, given by Cauchy’s principal value distribution }(1/(x À y)2 ). The appearance of both is elaborated in Appendix C (see Eqs. [C1–C7]). As a preliminary and very crude exposition, we can say that the d distribution represents a singular function that is zero everywhere except where its argument is equal to zero—there it is divergent. The Cauchy principal value distribution }(1/(x À y)2 ) behaves like the function 1/(x À y)2 , for (x À y)2 approaching 0 it is also divergent. We have to suspect, that such singular ‘‘functions’’ are not simply functions in the ordinary sense, their singular behavior and other features warrant a whole mathematical theory—their treatment is part of the theory of distributions as introduced by Schwartz (83) (see also Refs. 84 and 85). It would be far outside the scope of the present article to elaborate on this theory here; we will only pick those bits and pieces necessary to formulate the photon propagator and other Green functions. Functions or distributions with singularities are only one kind of infinity or divergence characteristic of quantum electrodynamics or, more generally, of quantum field theories. In QED, expressions that reveal divergent behavior can be submitted to procedures called renormalization or regularization, which allow us to calculate expectation values for physical quantities like energy, linear momentum, angular momentum, and others, which then turn out to be finite. One relatively simple example for such a regularization procedure, the ‘‘taming’’ of the singularities of d(x) and }(1/x), is carried out in Appendix C. In four-dimensional k space, the Fourier domain of space-time, we find for the photon propagator (see Appendix C, Eq. [C14]), Dmn F ðkÞ ¼ lim e!0 gmn k2 þie ¼ gmn } 1 k2   Àipdðk2 Þ   [34] In Eq. [34] we recognize, comparing it with Eq. [33], that the d and } distribution exchange their roles as far as the real and imaginary parts are concerned. We stress the point: Eqs. [33] and [34] represent the central result of this section and will provide us with the key characteristics for virtual photons. For our following discussion of Eqs. [33] and [34] it is worthwhile to introduce two technical concepts: (a) the concept of a lightcone in space-time and (b) the concept of a mass shell in momentum space. The technical definition of the notions of a lightcone and a mass shell is given in Appendix A (in particular, see Figs. A1 and A2), where it is shown that a fourvector u given in space-time can be one of three kinds, depending on its norm-square u2 . If u2 is positive, then vector u is referred to as time-like. For coordinate vectors x this means x2 ¼ c2 t2 À r2 > 0, from which follows c2 t2 > r2 . In other words, timelike coordinate vectors in space-time refer to propagation over distances r with a propagation speed below the speed of light, c, i.e., subluminal propagation, where r , c|t|. These vectors refer to points inside a region in space-time that forms a double cone with its apex at the coordinate origin (Fig. A1). There are time-like vectors in the forward cone for which t . 0 and in the backward cone for t , 0. Furthermore, there are vectors u in space-time, called space-like vectors, for which u2 , 0 holds. For coordinate vectors this becomes x2 ¼ c2 t2 À r2 < 0, consequently c2 t2 < r2 , referring to superluminal 282 ENGELKE Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a propagation. Finally, there are vectors u with u2 ¼ 0, called light-like vectors. Coordinate vectors x with x2 ¼ 0 are precisely those vectors that lie on the surface of the lightcone and it holds c2 t2 ¼ r2 , i.e., propagation with luminal speed c. The k space is characterized by the same metric properties as space-time. Thus, the Fourier domain of the time dimension x0 ¼ ct becomes the k0 dimension, which is frequency or energy. Likewise, the three spatial dimensions needed to specify a threedimensional position vector x have their Fourier domain counterpart in three k space dimensions with the momentum vector k. The relationship k2 ¼ 0, or equivalently o ¼ 2pc/l with frequency o and wavelength l of a freely propagating electro-magnetic wave or free photons (see Appendix A, Eqs. [A11, A12]) defines a spherical shell with radius k0 (Appendix A, Fig. A2) in three-momentum space. Those photons that satisfy the energy-momentum relationship k2 ¼ 0 are called on-shell, otherwise off-shell. Likewise, photons that travel exactly on the surface of the lightcone are called to be on the lightcone, otherwise off the lightcone. Now let us examine in detail the expressions in Eqs. [33] and [34]. In Eq. [33] we have the sum of two terms. The first term contains d((xÀy)2 ), which means that it contributes only for (xÀy)2 ¼ 0, (where Dirac’s d function becomes singular) to integrals like [21] or [22], i.e., the space-time difference vector xÀy is light-like, hence it describes propagation of photons on the lightcone, propagation with the speed of light, c. The second term in Eq. [33] constitutes Cauchy’s principal value }(1/((xÀy)2 )). This distribution is singular for (xÀy)2 ¼ 0 (i.e., on the lightcone), but it is also different from zero for (xÀy)2 , 0 as well as for (xÀy)2 . 0, i.e., for time-like as well as for space-like distances xÀy in space-time. Hence this term formally describes propagation off the lightcone! Turning our attention to Eq. [34], we find again two terms: d(k2 ) contributing only for k2 ¼ 0, i.e., corresponding to photons on-shell, and }(1/k2 ) being singular for k2 ¼ 0, but contributing for k2 = 0 as well, hence allowing photons to be off-shell. We also recognize that in Eq. [33] the real part of the photon propagator, Re(DF(xÀy)), contains d((xÀy)2 ) while the imaginary part, Im(DF(xÀy)), contains }(1/((xÀy)2 )). In momentum space it is just the other way around, Re(DF(k)) gives }(1/(k2 )) while Im(DF(k)) contains d(k2 ). These findings are illustrated in Fig. 4. In this figure propagation on the lightcone (with d((xÀy)2 )) is symbolized by a sharply drawn diagram. In contrast, propagation off the lightcone [characterized by }(1/((xÀy)2 ))] is drawn as a slightly fuzzy lightcone symbolizing that propagation may deviate from the lightcone surface. Likewise in momentum space: being off-shell (with }(1/(k2 ))) is symbolized by a sphere with unsharp boundary, being on-shell (d(k2 )) by a sharply drawn sphere. We further recognize that a sharp lightcone corresponds to an unsharp momentum sphere and vice versa, a sharp momentum sphere has an unsharp lightcone as its Fourier counterpart. We summarize these results once more in Table 1 where we also provide a first interpretation. As discussed before with Eq. [32], the photon propagator DF yields virtual photons, i.e., photons that are emitted and reabsorbed, and between these two events they propagate through space arbitrating the interaction between emitting and absorbing current densities. But now apparently we have found two kinds of photons to which we referred to in Table 1 as Figure 4 Pictorial illustration of the Fourier transform relationships as expressed in Eqs. [33 and 34] and Table 1. The real part of DF(x) characterizes propagation strictly on the lightcone indicated by a sharply drawn lightcone surface, corresponding to off-shell positioning in k space, as given by the real part of DF(k), symbolically indicated by a sphere with fuzzy surface. Likewise, off-lightcone propagation described by the imaginary part of DF(x) is illustrated by an unsharp lightcone, and on-shell positioning as given by the imaginary part of DF(k) pictured by a k sphere in 3D momentum space with sharp radius k0. Re(DF(x)) and Re(DF(k)) are Fourier transforms of each other. The same holds for Im(DF(x)) and Im(DF(k)) also forming a Fourier transform pair. VIRTUAL PHOTONS IN MAGNETIC RESONANCE 283 Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a virtual photons and asymptotically free photons, either being on the lightcone or off the lightcone in space-time, or equivalently, being off-shell or onshell in k-space, respectively. In a general setting, the distinction of virtual photons and asymptotically free photons on the basis of analyzing Eqs. [33, 34] has been suggested in a article by Castellani, et al. (94). The peculiarity of two types of photons needs an explanation that involves (i) Heisenberg’s uncertainty relations for the virtual photon exchange and (ii) an iteration of the argument related to the imaginary part of DF(xÀy) to explain the probabilistic appearance of asymptotically free photons. Ad (i) In a general setting, as regards the uncertainty relations for quantum mechanical observables expressed by (Hermitian) operators F and G acting on state functions f that are elements of a Hilbert space, we have the general relationship DFDG ! ð1=2Þjh½F; GŠij for the standard deviations (uncertainties) DF ¼ ||(FÀhFi) f || and DG ¼ ||(GÀhGi) f ||, which follows from Schwarz’ inequality valid for state functions in Hilbert space (e.g., Ref. 98, pp. 191). The notation h. . .i indicates the quantum expectation value and [F, G], as usual, denotes the commutator of the two operators F and G. The symbol ||f|| stands for the norm (which is a real, positive number for f = 0) of the state function f. Hence the expression ||(FÀhFi) f || denotes the norm of the state function that we get as a result when applying the operator (FÀ hFi) to f. As an example, we could take the position coordinate X (as an operator) and the operator of three-momentum component Px and with the commutator ½X; PxŠ ¼ i"h we arrive at the well-known position-momentum uncertainty relation DXDPx ! "h=2. If we want to apply the same ‘‘recipe’’ to the physical quantities energy and time to infer how energy and time uncertainties are related to each other, we face a serious obstacle: while energy E appears as an operator, it is the Hamiltonian of the system considered, time t is just a parameter, a coordinate in space-time. There is no time operator, neither in orthodox nonrelativistic quantum mechanics nor in quantum electrodynamics! Nevertheless, the question of the validity of an energy-time uncertainty relation DEDt ! "h=2 is entirely reasonable as long as we can provide a physical meaning for the time interval Dt. To further clarify this meaning of Dt, let us return to the accepted uncertainty relation DE DG ! (1/2) |h[H,G]i | involving the energy uncertainty DE, with G equal to an arbitrary Hermitian operator, and H equal to the Hamiltonian. Denoting by _G the operator for ‘‘change of G over time,’’ then the equation of motion reads _G ¼ ði="hÞ½H; GŠ þ qG=qt. If we suppose that G does not depend explicitly on time, then _G ¼ ði="hÞ½H; GŠ and we are allowed to write DEDG ! ð"h=2Þh _Gi. Now, due to Ehrenfest’s theorem (Ref. 98, p. 210) it holds h _Gi ¼ dhGi=dt, such that DEDG ! ð"h=2Þjdi=dtj. Let us define the time duration Dt ¼ DG dhGi dt       [35] which can be understood as that time interval it takes for the expectation value hGi to change in time by a value as large as the uncertainty DG, or to change over time and take all values within the range DG. With this definition for the time interval Dt, it directly follows the energy-time uncertainty relation DEDt ! "h=2. Now with Eq. [35] providing a meaning to the ‘‘time uncertainty’’ Dt, we may claim, for example, that DEDtx ! "h=2 where in this case G represents the position operator X (for one dimenTable 1 Characteristics of the Real and Imaginary Parts of the Feynman–Green Function in Space-Time and k Space Representation and Their Interpretation in Terms of Virtual and Asymptotically Free Photons Feynman-Green Function DF Real Part of DF Imaginary Part of DF Minkowski space-time, coordinates x, y À 1 4p dððx À yÞ2 Þ does propagate on the lightcone þ 1 4p2 } 1 ðxÀyÞ2   may propagate off the lightcone Four-dimensional momentum space, Coordinates k þ}ð1=k2 Þ positioned off-shell Àpd(k2 ) positioned on-shell Interpretation Virtual photons travel on the lightcone, i.e., (xÀy)2 ¼ 0, but they may be off zero-mass shell, k 2 = 0 Asymptotically free photons may travel off the lightcone, i.e., (xÀy)2 = 0, but they are on zero-mass shell, k 2 ¼ 0. Associated solution of the wave equation Inhomogeneous solution, interacting fields Homogeneous solution, free fields 284 ENGELKE Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a sion), further DG ¼ r is given by a distance, such that for a virtual photon propagating with velocity dhGi=dt ¼ dhXi=dt ¼ c on the lightcone we arrive at Dtx ¼ r/c and may interpret Dtx as the average lifetime (the propagation time) between emission and absorption of the virtual photon with the associated energy uncertainty DE. Nonetheless we emphasize, that this is just one possibility depending on the choice of the operator G ¼ X. Alternatively we may take G ¼ P with P equal to the three-momentum (again in one dimension), then we obtain Dtp ¼ DP/Fp with the force Fp equal to the total time derivative of the expectation value hPi for the momentum P. As we see here, the duration Dtp refers to the time derivative of the expectation value of operator P and thus has a different definition and meaning as compared to Dtx, because now it is related to the operator P instead of X. Summarizing, the time duration Dt appearing in the energy-time uncertainty relation DEDt ! "h=2 depends on the choice of the operator G, generally noncommuting with the Hamiltonian H. For short, G specifies Dt, see Eq. [35]. It should be clear by now that the question of the energy uncertainty DE for a virtual photon depends on the second observable G that we may want to consider for a measurement, as an experimental boundary condition. Suppose we know the precise distance r (obtained by some measurement) between emission and absorption, the energy uncertainty for the virtual photon is equal to DE ! "hc=ð2rÞ. But we keep in mind that this is only one possibility. For example, as we will investigate later in Section ‘‘Spin Current Density, Zeeman Hamiltonian, and Larmor Precession’’ when looking at Larmor precession through the QED view frame, we may face the situation that, for some additional reason, DE goes to zero, i.e., we may know that the virtual photon has a sharp or certain energy. For this case it follows that we are not allowed to interpret the duration Dt as arising from a certain propagation distance r, instead we have to take Dtp ¼ DP/Fp with the uncertainty DP of the photon’s three-momentum going towards infinity, or Fp going to zero, in such a way that still DEDtp ! "h=2 holds. The fact that here in our example we focus on the three-momentum P as possibly being entirely uncertain (DP becoming infinite) with an associated time interval Dtp going towards infinity, does not contradict the situation that the virtual photon travels the propagation distance r during the time interval r/c ¼ Dtr on the lightcone. It is just that Dtp = Dtr and in the case of sharp energy E the energy-time uncertainty relation has to be written down with the time interval Dtp, not Dtr. As we also can see, there is no contradiction with the statement that virtual photons are off-shell: the photon energy may have a sharp value, i.e., the zero-mass shell has a sharp radius, while the three-momentum is entirely uncertain. For a discussion on the notion of the uncertainty with respect to the Fourier transformation in relation to magnetic resonance we refer to Ref. 86. Ad (ii) As discussed earlier with Eqs. [31, 32] and with the introduction of the probability amplitude Z, the Feynman propagator as expressed in Eq. [33] also includes the transition for a photon being emitted and not being reabsorbed yet (and maybe it never will be reabsorbed) within a given time interval, or a photon being absorbed but with the uncertainty at which time it has been emitted (and, perhaps, it never was). The positivity requirement for the photon energy led to a complex-valued action functional W. The associated probability amplitude for photon propagation is equal to Z ¼ exp(iW) where the probability character is governed by the imaginary part of W. Table 1 lists virtual photons as those which, within a given time interval x0 Ày0 , are emitted and reabsorbed. All other photons are asymptotically free in the sense that either emission or absorption has not taken place yet within this specified time interval. In the literature these asymptotically free photons are sometimes referred to as real photons. We prefer not to use the term ‘‘real photon’’ here, because in real interactions virtual photons appear to be just as real as asymptotically free photons. Nevertheless, as pointed out in expression [31], the Feynman propagator DF(xÀy) as a whole characterizes the travelling path or trajectory of photons, but these trajectories appear to be ‘‘fuzzy trajectories,’’ the fuzziness given by the term }(1/ ((xÀy)2 )), which is the imaginary part in the action functional W. This uncertainty does not only cover the trajectory between their beginning (emission) and end points (absorption), it also includes these initial and end ‘‘points’’ themselves. When discussing Eq. [16], where we have restricted the frequency or energy range for photons to be positive (including zero), thus making a restriction in k0 space by reducing the energy value range from À1 . . . þ1 to a smaller subrange of 0 . . . þ1, the price to pay when doing this is that we got time dispersion, the associated uncertainty is Dt as specified by Eq. [35]. An increasing uncertainty Dtr for the propagation time also includes the possibility that within a given time interval no emission or no reabsorption may take place. If this happens to be the case for increasingly long, or asymptotically long time intervals, then the corresponding photons are asymptotically free, either when looking towards the past (backward lightcone) VIRTUAL PHOTONS IN MAGNETIC RESONANCE 285 Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a or looking towards the future (forward lightcone). Thus the photon propagator DF includes or admits the possibility, that exchanging photons escape from their fate of otherwise being caught as truly virtual and going forth and back between the interaction partners. The probability for a photon to succeed in escaping to ‘‘asymptotic freedom’’ is different from zero and can be computed from DF and by taking the interacting current densities into account. We will perform the calculation of such an escape probability (Eq. [57]) when discussing a specific NMR probe model in the next section. Last but not least, with the dichotomy in Table 1 we are reminded of the distinction well-known in classical electromagnetism: near field and far field. The near field is considered as the electromagnetic field in a region with distances from the source below (or small compared to) one wavelength for a given field mode. The far field is found at distances at or larger than one wavelength. There is no sharp boundary between near and far field, the transition from near to far field is gradual. Asymptotically free photons may escape to the far field, or more precisely, they may constitute the far field. Likewise, virtual photons should belong to the near field. The interpretation of virtual and asymptotically free photons outlined above will be applied to all electromagnetic phenomena discussed in the following. From Table 1 we may derive a useful means of recognizing the signature of the presence of virtual photons. Apart from using the general definition that in QED virtual photons mediate the electromagnetic interaction, the following indicator points to the appearance of virtual photons: the free-photon energy-momentum relationship k2 ¼ 0 does not hold (see Appendix A, Eq. [A10] and Fig. A2), i.e., virtual photons are offshell. Let us review briefly some examples: (i) In structures with wave compression (which means k2 , 0) like helical waveguides or solenoidal coils (87), there it is the interaction of one part of the structure with another part of the same structure, for instance two neighboring coil turns or a space-periodic repetition of structural elements like coil turns, that signifies an exchange of virtual photons. In this sense, wave compression is understood as l=c < 2p=o, i.e., we have o2 =c2 < 4p2 =l2 and consequently we arrive at o2 =c2 À 4p2 =l2 ¼ ðk0 Þ2 À jkj2 ¼ k2 < 0: Classically we may say that the geometric boundary conditions of wave propagation are different from those in free space. Using the language of QED we may say that virtual photons, appearing because of geometric boundary conditions not present in free space, govern the wave propagation, which is different from the free space propagation characterized by asymptotically free photons. (ii) Another example where k2 = 0 occurs in electromagnetic fields interacting with dielectric materials. Here, we encounter interactions between the electromagnetic field and the bound electric charges or electric dipoles in these materials. Macroscopically we find again wave compression: for example, a standing wave in an resonating transmission line filled with a dielectric material with er . 1 experiences a compression of its effective wavelength. (iii) Static interactions typically lead to k0 ? 0 (see our discussion of the Larmor precession in Section ‘‘Spin Current Density, Zeeman Hamiltonian, and Larmor Precession’’), i.e., the zero-mass shell degenerates to a point in k space and every photon with |k|2 . 0 must be virtual. A QED NMR PROBE MODEL: PULSED NMR AS A SCATTERING PROCESS In the previous two sections the basic understanding of how to interpret the Feynman-Green function, or synonymously, the photon propagator has been introduced. In the following, we want to apply and illustrate the basic concepts in a model that has relevance for pulsed NMR spectroscopy. Among all the parts of an NMR spectrometer it is the NMR probe whose design is based on the interaction between the spins in a sample and the radiofrequency (rf) electromagnetic field produced or received by the probe. In their 2002 article (55) on pulsed magnetic resonance with full quantization of the rf field, Jeener and Henin propose a probe model that is well suited to the task of describing NMR in QED terms. Their model decomposes the rf electromagnetic field into two parts: the free field and the bound field. The ‘‘free’’ field corresponds to the (undamped) eigenmodes of the probe circuitry including the transmission line connecting probe with the transmitter or the receiver. The bound field, in Jeener and Henin’s terms, is associated with the NMR sample. To avoid modeling the losses that occur in any real probe, which would lead to dissipation, the probe and the transmission line are 286 ENGELKE Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a assumed to be loss-free but with a length of the transmission line (whose characteristic impedance acts as a load to the circuit) being sufficiently large to ensure a large propagation time for the pulse. As a consequence such an incident rf pulse—propagating from the transmitter to the NMR coil or resonator (containing the sample), reflected there and travelling back as an outgoing pulse—can be considered as an event like a bypassing perturbation and, within a certain time interval in the model, the pulse is supposed to not re-appear in the probe. In this sense, we are actually allowed to view the rf pulse as being scattered by the spins in the sample with the incoming pulse as arising from some asymptotic initial condition in the past and the outgoing pulse disappearing with some asymptotic final condition in the future. This strongly idealized model is sketched in Fig. 5. On the basis of the decomposition into a free field and a bound field, Jeener and Henin provide a discussion of the quantization of the electromagnetic field within this model by setting up an ad hoc Hamiltonian that provides a link between the fully quantized scheme with the classical scheme based on Bloch’s equations. Although we will make use of the above principal probe model here as well, we will choose a different approach to introduce the QED view into NMR. We want to consider the following situation: first, let us suppose that the electromagnetic four-potential associated with the incident pulse, denoted by Am in, is given as a quantum field. Please remember that the superscript m in Am in is a contravariant index that counts components, m ¼ 0, 1, 2, 3, while here the subscript ‘‘in’’ indicates the incoming field. Second, when the incoming pulse arrives at the NMR sample region inside the NMR coil, it starts interacting with the spins inside the sample. Third, after the pulse travelled through the NMR coil and sample region, it leaves as outgoing pulse, where now, of course, the field of the outgoing pulse, symbolized by Am (t,x), has been changed as compared to Am in. It is as if the incident pulse has collided with or has been scattered by the spins in the sample, the latter represented by a current density jn (y), and the associated electromagnetic interaction has changed the overall field. Since we have not allowed dissipation in our model, we may claim that the scattered field Am (t,x) is related to the field Am in of the incident pulse by a unitary transformation, Am ðt; xÞ ¼ UðtÞAm inUþ ðtÞ [36] with the field operator Ain in [36] referring to the incoming electromagnetic pulse an (asymptotically) long time before it arrives in the spin sample region. The time evolution operator U(t) is given as the unitary operator Figure 5 Schematic model of an NMR probe for pulsed NMR similar to those proposed by Jeener and Henin in Ref. 55. An incident rf pulse generated by the rf transmitter travels over the transmission line, through the circuit to the NMR coil or resonator where it is reflected and travels back through the circuit and transmission line. The NMR sample containing the spins (not shown) is situated inside the coil or resonator and represents a spin current density which interacts with the incident pulse. The result of this interaction is the outgoing pulse followed by the FID signal, the latter is routed to the receiver (this usually happens in the preamplifier, which is here thought as part of the receiver). The coil/resonator and the circuitry are enclosed by a shielding tube. The rf electromagnetic field can only enter and exit through the long transmission line. VIRTUAL PHOTONS IN MAGNETIC RESONANCE 287 Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a UðtÞ ¼ T exp Ài Zt À1 dt0 Hintðt0 Þ 0 @ 1 A [37] with the interaction Hamiltonian Hintðt0 Þ ¼ Z d3 yAm inðy; t0 Þjmðy; t0 Þ [38] where now Am inðy; t0 Þ refers to the field during the scattering process in the region characterized by position vectors y for the spins in the sample. Dyson’s time-ordering operator T, defined by Eqs. [30], appears in Eq. [37] because, in general, the interaction Hamiltonian does not commute with itself at different time instants. We have introduced the interaction between spins and electromagnetic field in a fairly general manner. The product Am inðy; t0 Þjmðy; t0 Þ in the integrand in Eq. [38] representing a Hamiltonian density describes in a universal manner the electromagnetic coupling between any current density and the electromagnetic field, as we have convinced ourselves in Section ‘‘The Feynman Propagator,’’ Eq. [23]. To specialize to the case of magnetic resonance, one has to characterize the current density jn ðy; t0 Þ that represents the spins. We will derive that spin current density later on in Section ‘‘Spin Current Density, Zeeman Hamiltonian, and Larmor Precession,’’ where we also show that jn ðy; t0 Þ may represent a function although we treat the spin particle quantum mechanically. So far, we have taken account of the action of the rf field pulse Ain(x) to the spin system and the action of the spin system on the rf field, during the pulse. After the pulse has propagated through the sample region, then some pastpulse response of the spin system—the free induction decay, FID—appears. For the case of a single-spin FID, we look more closely in Section ‘‘Single-Spin FID: NMR Radiation Damping.’’ Now Eq. [36] is supposed to tell us in detail how the electromagnetic four-potential of the incident pulse is changed by the interaction with the spins in the sample or, so-to-say, by the scattering process. The time evolution in U(t) covers a time interval from an (infinitely) far past or, in practice, a sufficiently far past when there is not yet any interaction between incoming pulse and spin system, yet, lasting to a time instant labeled by t. This instant t can be situated in the interval during which the interaction happens, but also before or afterwards, taking into account that the Hamiltonian density Am inðy; t0 Þjmðy; t0 Þ itself is dependent on space position and time. In the following, starting from Eq. [37], we want to derive an expression for the time evolution operator that contains the photon propagator DF, such that we may be set in a position to analyze the appearance of virtual and asymptotically free photons within the probe model for pulsed magnetic resonance. To achieve this goal, we will proceed by focusing on the incoming and outgoing pulse, which propagate through the rf coil or resonator and interact with the spins. The unitary time evolution operator U(t) transforms the incident quantum electromagnetic field pulse Am in into a quantum field that includes the effect of propagation through the probe and also includes interactions with the current density jn ðy; t0 Þ of the spins. Hence, taken from Eqs. [37, 38], we begin with UðtÞ ¼ T exp Ài Zt À1 dt0 Hintðt0 Þ 0 @ 1 A ¼ T exp Ài Zt À1 dt0 Z d3 yAn inðy; t0 Þjnðy; t0 Þ 0 @ 1 A ½39Š To introduce the virtual-photon picture by re-establishing the role of DF in the time evolution operator [39], we have to consider a factorization of U(t) that allows us to view time ordering (as signified by Dyson’s time ordering operator T) of operators of the electromagnetic field as retardation in the propagation process of electromagnetic fields. After performing this first step and familiarizing ourselves with the concept of normal ordering of field operators, we will be in a position to derive an expression for U(t), which contains the photon propagator DF. These steps, beginning with the factorization of U(t), are presented in detail in Appendix D; the result of the first step (see Eqs. [D1–D10]), which relates U(t) to retardation, is UðtÞ ¼ exp Ài Zt À1 dx0 Z d3 xAn inðxÞjnðxÞ 0 @ 1 A  exp À i 2 gmn Zt À1 dx0 Z d3 x 0 @  Zt À1 dy0 Z d3 yjmðxÞDretðx À yÞjnðyÞ 1 A ½40Š One crucial assumption made in the derivation of Eq. [40] is that the current densities jm(x) and jn(y) are functions, not operators. This may happen, if we would treat them as classical current densities. But also in the case of particles obeying ordinary quantum mechanics (first quantization), current densities are functions as we will see later on. The assumption 288 ENGELKE Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a of current densities being functions, not operators, restricts the generality of [40] and all expressions that depend on it. The consequences will be discussed at the end of this section and more thoroughly in Section ‘‘Interaction of a Spin-1/2 Particle with External Time-Harmonic Fields.’’ Equation [40] represents a noteworthy result. Comparing it with Eq. [39], it tells us that time-ordering, symbolized by the time-ordering operator T in Eq. [39], translates into a multiplicative exponential term in Eq. [40] with an integral in the exponent containing the retarded propagator. Thus time-ordering transforms into time-retardation. The first exponential term in Eq. [40] contains the unitary operator part, with the Hermitian field operator Ain(x) in the exponent. Furthermore, in the interpretation of Eq. [39] we were clear about the physical meaning of the field operator Am in(y) and the current density jm(y). The operator Ain(y) stood for the four-potential of the quantized incident field pulse within the spatial region y of the spin particles while j(y) represented the current density of the spin particles themselves. In the second term of Eq. [40] there are now two current densities, j(x) and j(y), the interaction between both mediated through the retarded propagator Dret(xÀy). Although jm(y) still represents the spins in the sample, we now have to admit that j(x) must signify the rf current in the circuit and the coil of the probe. The retarded four-potential of the incident pulse, An;retðxÞ ¼ 1 2 Zt À1 dy0 Z d3 yDretðx À yÞjnðyÞ; [41] acting in the spatial region x where the rf current density is to be found, is generated by the spin current density j(y). Hence Eq. [40] could be written as UðtÞ¼exp Ài Zt À1 dx0 Z d3 xðAn inðxÞÀAn retðxÞ1ÞjnðxÞ 0 @ 1 A [42] with the field (operator) Ain(x) generated by the rf current and Aret(x) produced by the spin current and being retarded. 1 denotes the unity operator. An important observation should be made, namely, the four-potential Aret(x) expressed by Eq. [41] is not an operator of the electromagnetic field anymore—in terms of field variables it represents a function. The detailed properties of jn (except that they have to be functions) are still left open and will be treated below. The field operator part for the time evolution operator characterizing the quantum evolution of the electromagnetic field is taken over by the first exponential term in Eq. [40]. So far we have managed to express U(t) in [40] via the retarded propagator Dret, indicating the inherent time-ordering requirement in Eq. [39]. Proceeding further from Eq. [40], U(t) can be expressed via the photon propagator DF. For that purpose we define the shorthand notation : . . . : by : exp Ài Zt À1 dx0 Z d3 xAn inðxÞjnðxÞ 0 @ 1 A : ¼ exp Ài Zt À1 dx0 Z d3 xAnÀ in ðxÞjnðxÞ 0 @ 1 A  exp Ài Zt À1 dx0 Z d3 xAnþ in ðxÞjnðxÞ 0 @ 1 A ½43Š called normal-ordered product, where we have used (see Eq. [24]) the positive-frequency part including the photon annihilation operator of the four-potential, given as A mðþÞ in ðxÞ ¼ Z d3 k ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 2pð Þ3 2ok q X3 l¼0 emðlÞ ðkÞaðlÞ ðkÞeÀikx [44] and the negative-frequency part with the photon creation operator, A mðÀÞ in ðxÞ ¼ Z d3 k ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 2pð Þ3 2ok q X3 l¼0 emðlÞ ðkÞaðlÞþ ðkÞeikx [45] From [44, 45] we recognize that when we expand the two exponentials on the right-hand side of [43] in a power series, normal ordering results in an arrangement of creation and annihilation operators in product terms such that all creation operators aþ are always to the left of all annihilation operators a appearing in that product. Thus, products like aþ a or aþ aþ a are normal-ordered, while aaþ or aþ aaþ are not. With these definitions, as shown in detail in Appendix D, Eqs. [D11–D17], Eq. [40] leads to UðtÞ ¼ : exp Ài Zt À1 dx0 Z d3 xAn inðxÞjnðxÞ 0 @ 1 A : exp À i 2 Zt À1 dx0 Z d3 x Zt À1 dy0 0 @  Z d3 yjmðxÞDmn F ðx À yÞjnðyÞ  ½46Š VIRTUAL PHOTONS IN MAGNETIC RESONANCE 289 Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a Equation [46] formally achieves our goal of expressing the time evolution operator U(t) via the photon propagator DF(xÀy). However, as written in Eq. [46], we have some preliminary price to pay: U(t) on the left-hand side is supposed to be a unitary operator. The exponential containing DF in the exponent is not an operator or operator function related to the electromagnetic field variables and the normal-ordered exponential operator : . . .: taken separately by itself is not unitary. For the sake of demonstration, how can we convince ourselves that the entire righthand side of Eq. [46] fulfills the condition of unitarity? For that purpose we insert Eqs. [33, 43] into [46], such that we see all separate factors explicitly written out, UðtÞ¼exp Ài Zt À1 dx0 Z d3 xAnÀ in ðxÞjnðxÞ 0 @ 1 A Âexp Ài Zt À1 dx0 Z d3 xAnþ in ðxÞjnðxÞ 0 @ 1 A Âexp þ i 2 Zt À1 dx0 Z d3 x Zt À1 dy0 0 @  Z d3 yjmðxÞ gmn 4p2 pdððxÀyÞ2 ÞÀi} 1 ðxÀyÞ2 !" # jnðyÞ ! In the third exponential we detach the real and imaginary parts of DF into separate factors—this is possible if j(x) and j(y) commute—such that we obtain UðtÞ ¼ exp Ài Zt À1 dx0 Z d3 xAnÀ in ðxÞjnðxÞ 0 @ 1 A  exp Ài Zt À1 dx0 Z d3 xAnþ in ðxÞjnðxÞ 0 @ 1 A  exp þ 1 2 Zt À1 dx0 Z d3 x Zt À1 dy0 0 @  Z d3 yjmðxÞ gmn 4p2 } 1 ðx À yÞ2 ! jnðyÞ !  exp þ i 2 Zt À1 dx0 Z d3 x Zt À1 dy0 0 @  Z d3 yjmðxÞ gmn 4p dððx À yÞ2 ÞjnðyÞ  ½47Š We see that that the imaginary part of DF (containing i times the principal value distribution }) gives rise to an exponential with real-valued exponent. Introducing the amplitudes aðk; x0 Þ ¼ ÀiemðlÞ ðkÞJmðk; x0 Þeikx0 ; aðk; tÞ ¼ Zt À1 dx0 aðk; x0 Þ ½48Š containing the three-dimensional k space Fourier transform of the four-current density, Jmðk; x0 Þ ¼ Z d3 x expðik Á xÞjmðx; x0 Þ [49] and confining ourselves to the case where the currents generate only a single mode k of the electromagnetic field with polarization l, we may derive from [47] (see Appendix D, Eqs. [D18–D25] UðtÞ ¼ exp aðk; tÞaþ ðkÞ À aà ðk; tÞaðkÞð Þ Â exp i 8p Zt À1 dx0 Z d3 x Zt À1 dy0 0 @  Z d3 yjn ðxÞdððx À yÞ2 ÞjnðyÞ 1 A ½50Š where we have omitted the integral over momentum space and where now k is referring to one specific field mode. The restriction to one field mode is not really a strong restriction of generality here, because in all terms and expressions of U that contain the amplitudes a(k,t) we may reintroduce multiple modes by writing again the integral over d3 k, see Appendix D, Eqs. [D24, D25]. Nevertheless writing down the expressions only for one mode makes the notation less bulky and easier to read. The first exponential in Eq. [50] represents Glauber’s displacement operator (see Refs. 4, 5, and 97), DaðtÞ ¼ exp aðk; tÞaþ ðkÞ À aà ðk; tÞaðkÞð Þ ¼ expðaaþ Þ expðÀaà aÞ expðÀaaà =2Þ ½51Š where on the right-hand side in the second equation of [51] we have omitted the arguments k and t. Thus for Eq. [50] we may write UðtÞ ¼ DaðtÞ exp i 8p Zt À1 dx0 Z d3 x Zt À1 dy0 0 @  Z d3 yjn ðxÞdððx À yÞ2 ÞjnðyÞ 1 A ½52Š 290 ENGELKE Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a So starting from the general, time-ordered expression [39], passing through Eq. [40], which provides a link to the retarded propagator, arriving first at Eq. [46], which expresses U(t) via the photon propagator, we finally arrive at Eq. [52], which represents U(t) as a product of Glauber’s displacement operator Da(t) and an exponential that contains the real part of the photon propagator, i.e., it contains the d function d((xÀy)2 ) indicating photon propagation on the lightcone. The imaginary part of DF has been subsumed into the operator Da(t). Hence we are led to the conclusion that Glauber’s displacement operator represents asymptotically free photons (being on-shell) appearing in the incoming or outgoing rf pulse, while the exponential containing the real part of DF stands for the virtual photons being exchanged between the current density in the circuit, resonator, or coil and the spin current density. By power series expansion of the displacement operator Da(t) we can easily convince ourselves that the adjoint operator associated with Da(t) is equal to Dþ a ðtÞ ¼ DÀaðtÞ and from Eq. [51] it follows then, that DaDþ a ¼ Dþ a Da ¼ 1, i.e., the displacement operator Da is, indeed, unitary. For multiple modes this argument stays valid, because creation and annihilation operators, belonging to different modes, commute (Eq. [25]), which allows us to factorize Da and each factor Dak for each mode k is unitary by itself. Also by using the power series expansion for the unitary operator Da, we obtain the commutator relationships ½aþ ; DaŠ ¼ aà Da; ½a; DaŠ ¼ aDa. These yield, when left-multiplying by Da þ : DaðtÞaþ Dþ a ðtÞ ¼ aþ À aà ðtÞ; DaðtÞaDþ a ðtÞ ¼ a À aðtÞ ½53Š From Eqs. [53] the name displacement operator for Da becomes clear: performing a unitary transformation of the photon creation operator aþ or the photon annihilation operator a by means of Da results in a displacement by a* or by a, respectively. The Fourier expansion of field operators, Eq. [24], and the property of Da expressed by [53] lead us to conclude DaðtÞAm ðt;xÞDþ a ðtÞ ¼ Am ðtþt;xÞÀAm a ðt;xÞ; Am a ðt;xÞ ¼ aðk;tÞeÀikx þaà ðk;tÞeikx ; x ¼ ðct;xÞ ½54Š Thus time evolution via Da changes the quantum field Am(x) by displacing the time coordinate and displacing it by the field Am a (x) that depends on the current densities involved in the interaction. When we apply Da to the photon vacuum state |0i, we create a new state (4) jaðtÞi ¼ DaðtÞj0i [55] In order to characterize this time-dependent state |a(t)i, we note first that it can be expanded in a basis of Fock states |ni as follows (4) jaðtÞi ¼ X1 n¼0 hnjaijni ¼ eÀ1 2aaà X1 n¼0 an ðtÞ ðn!Þ1=2 jni [56] which can be verified by using the power series expansion for Da(t) given in Eq. [51]. States |a(t)i defined by Eq. [56] are called coherent states. Since they represent a superposition of Fock states, they are not eigenstates of the photon number operator, i.e., coherent states are characterized by an uncertainty of the photon number in the field. Another interesting feature of these states is that |a(t)i represents an eigenvector of the incident-field photon annihilation operator a(k), aðkÞjai ¼ ajai, associated with the time-dependent eigenvalue a(t). Note, the photon annihilation operator a(k) is not Hermitian and a(t) is a complex number. From Eq. [56] we can compute the probability to find exactly n photons in the field that is in coherent state |ai, i.e., the square of the transition amplitude hn|ai, paðnÞ ¼ jhnjaij2 ¼ eÀjaj2 jaj2n n! ; jaj2 ¼ aaà ¼ "n [57] We recognize in [57] a Poissonian distribution with "n being the average number of photons in the field being in coherent state |ai, while the width (standard deviation) of this distribution is equal toffiffiffi "n p . In mathematical statistics the Poisson distribution appears as a limiting case of the Bernoulli or binomial distribution pn;z ¼ z n   pn ð1 À pÞzÀn [58] stating the probability pn,z for an event X to occur n times in a number z of independent trials, where the probability for X to occur in an individual trial is equal to p. For the specific case where this individual probability is very small, p ( 1, one obtains pn;z ¼ ðzpÞn n! expðÀzpÞ [59] which is identical to Eq. [57] when we set "n ¼ zp. Hence we may interpret Eq. [57] as providing the probability for the emission (the event X) of n photons, e.g., in a number z of consecutive time interVIRTUAL PHOTONS IN MAGNETIC RESONANCE 291 Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a vals, or alternatively by a number z of independent nuclear or electron spins, where the individual probability p that one photon is emitted (in a given time interval or by a given spin) is small compared to unity. The average number of photons emitted is equal to "n ¼ zp, hence this average number, according to Eqs. [48, 49], depends on the current density in three-dimensional momentum space. Moreover from [57], the probability that no photons are emitted at all, p0 ¼ expðÀ"nÞ; [60] becomes larger, if the expectation or average value "n of the photon number becomes smaller. If we consider the time evolution (Eq. [36]) leading from the incident field into the interacting and outgoing field pulse, we realize that the exponential in [52] containing the real part of DF commutes with Am inðt; xÞ, because it does not contain any operator term that acts on electromagnetic field states. Thus Eq. [36] becomes Am ðt; xÞ ¼ DaðtÞAm inDþ a ðtÞ [61] Therefore Glauber’s displacement operator Da alone governs the time evolution of the field operators for the external incoming and outgoing field. Da depends on the time-dependent quantity a, which in turn depends on the k space current density Jmðk; x0 Þ, Eqs. [48, 49], representing the current density involved in the interaction of the incident rf pulse. Da includes the imaginary part of the photon propagator DF (see Eqs. [47–50]) that we connected with on-shell and off-lightcone photons. So the field Am ðt; xÞ of the interacting and outgoing pulse, according to Eq. [61], contains asymptotically free photons emitted by either the spin current distribution jm (y) or by the rf current jm(x). The detailed action of Da on the quantum field operator has been shown already in Eq. [54]—the associated unitary transformation leads to a displacement of the field operator Am in(x) by Am a (x). Note, Am a (x) is not an electromagnetic field operator anymore. Let us draw some conclusions from the findings in the current section for the NMR probe model: (i) The rf field of the incoming, interacting and outgoing pulse is generated by the rf current density in the circuit or resonator and interacting with the spin current density located in the sample. The time evolution operator for the field operators is given by Eq. [39]. (ii) For non-operator current densities, j(x) and j(y), we have found the single-mode electromagnetic rf field pulse in a coherent state |ai, characterized by an average photon number "n that depends on the integral over the current density in k space (Eqs. [48, 49]) and governed by a Poissonian probability distribution [57]. (iii) Coherent states |ai are linear superpositions of Fock states |ni (Eq. [56]), hence they are not energy eigenstates; more precisely, they are not eigenstates of the Hamiltonian for the free electromagnetic field. (iv) The time evolution [61] of field operators with the electromagnetic field in a coherent state |ai is governed by Glauber’s displacement operator Da, Eq. [51], which contains the normal-ordered product [43] and the imaginary part =mðDFðx À yÞÞ of the photon propagator (worked out in Eqs. [47–50] and Appendix D). Therefore the action of Da as time evolution operator for the electromagnetic field originates from asymptotically free photons (Section ‘‘Quantization of the Electromagnetic Interaction Field: Virtual Photons’’). (v) As it turns out, coherent states |ai are quasi-classical states. This means that the probability distribution [57], characterized by the average value "n and by the standard deviation ffiffiffi "n p (Poisson distribution), leads to a relative standard deviation offfiffiffi "n p ="n ¼ 1= ffiffiffi "n p which goes towards zero for very large average photon numbers. For the expectation value ha|(Am(x))2 |ai of the square of the four-potential with the field in coherent state |ai we find, according to [24] and remembering |ai as an eigenstate of the annihilation operator, as follows from Eq. [56], that ha|(Am(x))2 |ai ! "n. Hence, the relative standard deviation for Am(x) in the coherent state is proportional to 1= ffiffiffi "n p . The same applies to the electric field strength and the magnetic induction field strength computed from Am(x) (see Ref. 4). Therefore, the field strengths take on sharp average values, i.e., the relative standard deviations vanish, for large average photon numbers, i.e., in that case we are in the classical limit. Generalizing the above considerations to multiple modes, we recognize that the electromagnetic field with each mode in a coherent state |aki gives rise to a product state jfi ¼ Q k jaki which is still a quasi-classical state in the sense that the relative 292 ENGELKE Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a uncertainties of observables vanish in the classical limit, but it is not a coherent state as defined by Eq. [56] anymore (that means that for |fi the Poisson distribution does not apply). However, because |fi can be written as a product of coherent states, it holds that (a) a unitary time evolution operator can be derived as Df ¼ Q k Dak with Dak equal to Glauber’s displacement operator for mode k and that (b) this unitary operator Df acts still as the creation operator for the quasi-classical state |fi from the vacuum state: jfi ¼ Df j0i (Refs. 54, 55, and 97). One major supposition made in the derivations of the present section is that the current densities j(x) and j(y) are functions, not operators. In our probe model, j(x) represents the rf current density, and j(y) represents the spin current density. More specifically: j(x) corresponds to a current density of electrons in an conduction band of a metal that makes up the building material of coils or resonators and other circuit elements, while the spin current density j(y) specifically stands for the spin particles in the sample. Before we address these issues in more detail in Section ‘‘Interaction of a Spin-1/2 Particle with External Time-Harmonic Fields,’’ we will turn our focus in the next section to the question of how to specify the spin current density. SPIN CURRENT DENSITY, ZEEMAN HAMILTONIAN, AND LARMOR PRECESSION Although we have introduced electromagnetic fields generated by sources, we have not treated in any detail the sources themselves. We will begin to do so now in the present section with particular attention to the spin particle. As we have outlined in the introduction, we call particles Dirac particles in the strict sense, if their associated wave functions satisfy the Dirac equation when acted on by an external electromagnetic field, and if these particles do not undergo strong interactions. In the strict sense, the electron and the positron, the latter being the anti-particle associated with the electron, are Dirac particles. For these particles we have the following: (a) The Dirac equation allows us to predict that these particles have a magnetic moment originating from the spin angular momentum with spin quantum number of 1/2, hence they are fermions, (b) to within a high degree of accuracy, the Lande´ factor g can be calculated assuming a quantized electromagnetic field, and (c) the calculated g factor agrees very well with the experimentally determined value. Protons or compound nuclei with spin 1/2 are not Dirac particles in this strict sense. These particles have an internal structure whose components (quarks) interact with each other via strong nuclear forces that are not subject to quantum electrodynamics. The field theory for particles with strong interactions is QCD. Nevertheless, at low energies (as compared to the nuclear rest mass and as compared to nucleon-nucleon binding energies) and abstracting from nuclear structure by just considering them as nearly point-like particles with rest mass m and a given nuclear g factor—which however then cannot be inferred from quantum electrodynamics— they may be considered as Dirac-like particles in processes that describe only electromagnetic couplings between nuclei and electrons, or electromagnetic couplings among different nuclei. Therefore low-energy nucleus-electron interactions can be treated by quantum electrodynamics—such interactions appear, e.g., in the NMR chemical shift interaction or scalar couplings, in EPR fine structure or hyperfine structure couplings, or also as electromagnetic nucleus-electron couplings with measurements mediated by the rf electromagnetic field either generated by a macroscopic electron current through an rf coil or resonator acting on a nuclear spin-dipolar moment, or vice versa, the nuclear spin-dipolar magnetic field as inducing a Faraday voltage with a resulting electron current through an rf coil connected to an rf circuit. Even direct dipolar spin-spin couplings between two nuclei can be investigated in this way. In the present article we will not treat the Dirac equation with all its implications. For a brief introduction including definitions we refer to Appendices E and F, and the textbook literature (e.g., Refs. 21, 22, 79–82, 89, 90, and 93). Nevertheless, to continue with our discussion, we need one essential result concerning the density of a current of Dirac particles or Dirac-like particles—in the following let us refer to these particles jointly as spin-1/2 particles. As discussed above, electrons strictly obey Dirac’s equation. Protons do not do that, although protons can be characterized by the same principal mathematical form of the current density as for electrons. This general form can be derived for electrons from Dirac’s equation by demanding conditions that we expect to be fulfilled by any four-current density jk of spin-1/2 particles, notably the fulfillment of a continuity equation and the existence of a positive-definite time-like component j0 such that it can be interpreted as a probability density for the spin-1/2 particle. It reads jkðxÞ ¼ e"cðxÞgkcðxÞ [62] For more details on how to obtain [62] we refer to Appendices E and F, in particular to the result VIRTUAL PHOTONS IN MAGNETIC RESONANCE 293 Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a obtained in Eq. [F3]. The algebra behind Dirac’s equation requires that the Dirac matrices gk appearing in Eq. [62] are of dimension 4Â4 and the wave function c(x) represents an object called bispinor, having four components, each a function of spacetime coordinates x. A bispinor is a mathematical object which takes into account that the covariance of Dirac’s equation requires to tackle (a) the Lorentz transformation of space-time variables, and in juxtaposition, (b) the associated unitary transformation in Hilbert space of spin variables (21, 79, 81). An early, comprehensive investigation on the unitary representation of the inhomogeneous Lorentz group dates back to Wigner (99). In the past, NMR has been used to explicitly demonstrate the spinor character of spin- 1/2 nuclei and the rotational symmetries of spins-1/2 and spin-1 nuclei (100–103). The current density jk(x) represents a four-vector in space-time—it is not a bispinor. The quantity e is equal to the electric charge of the particle. In connection with the conditions mentioned above for the four-current density jk, note the following two features of the current density [62]: (a) jk(x) has vanishing four-divergence, i.e., qk jk ¼ 0. Using ordinary vector notation it becomes apparent that this represents a continuity equation (see Appendix A, Eqs. [A16, A31, A32]). Furthermore (b) the time-like component j0ðxÞ ¼ "cg0c ¼ cþ c of the current density is equal to the squared magnitude of c, hence positive definite, and can be interpreted as a probability density for the spin-1/2 particle. For the proper definitions of the bispinors c;"c;cþ we refer to Appendices E and F (Eqs. [E11, E12, F1]). Before going into technical details, one important remark has to be made here. For the electromagnetic field (given by four-potential functions) we have directly applied quantum field theory based on CCR’s and obtained quantum field operators An. We took the classical electromagnetic field and performed quantization. For spin-1/2 particles the initial situation is different ! The Dirac equation with the Dirac wave function c as the solution of the former is one possible relativistic generalization of the Schro¨dinger equation for a quantum particle. Thus here the function c does not indicate a proper classical field function as in the case of the electromagnetic field, rather c represents already a (multi-component) field function for the quantum spin-1/2 particle which allows a probabilistic interpretation. In order to arrive at a full quantum field theory including both, spin-1/2 particles and electromagnetic fields, one would have to quantize the field c as well (as if it were a classical field) by assigning operator character to c and require the fulfillment of anticommutation rules for these new field operators. In the present article we do not perform this field quantization (sometimes called second quantization) for the spin-1/2 particle wave function c. That means we treat spin-1/2 particles with wave functions c in analogy to nonrelativistic Schro¨dinger quantum mechanics, because we want to stay as close as possible to the ‘‘orthodox’’ spin particle picture as used in magnetic resonance. It is for that reason, that the current density jn in Eq. [62], with c representing functions and not operators, is a (vector) function as well. The requirement for the current density jn representing a function (and not an operator) is essential for the appearance of coherent states and quasi-classical states as discussed in Section ‘‘A QED NMR Probe Model: Pulsed NMR as a Scattering Process.’’ A short time after Dirac introduced his equation of motion, it could be shown that the current density [62] can be decomposed into two physically relevant parts. The first part represents the particle current resulting from the spatial motion of the particle and the second part originates from the spin of the particle. In the literature this decomposition is commonly referred to as Gordon decomposition (see Refs. 21, 91, 92, and Appendix F), jk ðxÞ ¼ e"cðxÞgk cðxÞ ¼ À e 2m "cðxÞðPk cðxÞÞ À ÀðPk "cðxÞÞcðxÞ À iPnð"cðxÞskn cðxÞÞ Á ½63Š In Eq. [63] we have introduced the momentum Pk ¼ pk À eAk of a particle situated in an electromagnetic field with the four-potential Ak (x) (m denoting the rest mass of the spin-1/2 particle and pk ¼ iqk designating the momentum operator for the free particle). In other words, we look already at an electromagnetic coupling between the particle and the external field. The prescription Pk ¼ pk À eAk to introduce the electromagnetic field into Dirac’s equation is called minimum coupling condition and can be understood as a direct consequence of gauge invariance of the electromagnetic field equation (Appendix B) with the concomitant phase invariance of Dirac’s equation (see for example, Ref. 10). As we recognize on the right-hand side of Eq. [63], the first contribution, consisting of the first two terms involving the linear momentum Pk only, may be considered as a ‘‘convection’’ or ‘‘conduction’’ current, arising from the motion of the Dirac particle in space. The second contribution is given by the third term in Eq. [63] and represents the spin current as signified by the spin tensor skn (Appendix F, Eq. [F12]). With an explicit expression like Eq. [63] for the current density, we are now in a position to describe 294 ENGELKE Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a the interaction of a spin-1/2 particle with an external electromagnetic field. The particle is characterized by a Dirac wave function c (x,s), where x denotes space-time coordinates and s stands for the spin variable. An external electromagnetic field is represented by the four-potential Am. The interaction Hamiltonian density reads Hintðx; sÞ ¼ jm ðx; sÞAmðxÞ ¼ e"cðx; sÞgm cðx; sÞAmðxÞ [64] The associated Feynman diagram, specified for the case of spin interaction, is depicted in Fig. 6, displaying a diagram similar to the one in Fig. 1(A). It shows an incident particle in the state c with spin angular momentum s ¼ L1, an outgoing particle in the state "c with spin angular momentum s ¼ L2 and an exchange of a photon between the source (shown as a small circle) of the external field and the particle. In Fig. 6 the time axis points in vertical direction upwards, but the arrows labeled with c and "c do not symbolize spatial motion. The diagram depicts a particle initially in spin state cðL1Þ, then exchanging a photon characterized by three-momentum K and angular momentum M with the source of the external field Am which leaves the particle in spin state "cðL2Þ. The energy density associated with this interaction is given by the Hamiltonian density [64]. Focus on the spin current, more specifically, the spin part of the current density for a single spin, as follows from [63] jm spin ¼ ie 2m Pnðcsmn cÞ [65] In [65] we want to separate jm spin into its timelike and spacelike components. Accomplishing this goal is somewhat tedious and lengthy and can be achieved best by calculating all components of the spin tensor smn (defined in Appendix F, Eq. [F12]), then assembling all component expressions together, and finally reading off the following result from the component expressions: j0 spin ¼ Àe 2m ðp À eAÞðjà sw À wà sjÞ; jspin ¼ e 2m ðp0 À eA0Þ Â ðjà sw À wà sjÞ½ þiðp À eAÞ Â ðjà sj À wà swފ ½66Š where ‘‘Â’’ denotes the ordinary cross product of vector analysis and where we have formally decomposed the bispinor c into two spinors j and w according to c ¼ c1 c2 c3 c4 0 B B @ 1 C C A ¼ j w   ; j ¼ j1 j2   ; w ¼ w1 w2   [67] and s ¼ ðs1; s2; s3ÞT denotes the ‘‘vector of Pauli 2Â2 spin matrices’’. Each of the quantities j and w is a spinor, hence the term bispinor for c. In order to find the bridge between the general physical formalism of spinors and associated current densities and the more familiar spin formalism utilized in magnetic resonance, we need to proceed in two steps. First, we have to make the passage to the nonrelativistic realm, i.e., the domain of low velocities as compared to c, low energies, low momenta, stable particles, excluding antiparticles. Second, we need to find a link between the notation with spinor wave functions and the more familiar nonrelativistic spin operator formalism that we encounter in magnetic resonance. Nonrelativistic Limit In the nonrelativistic limit—a precise definition is given in Appendix F, Eqs. [F23]—the magnitude of the spinor w becomes small compared to that of the spinor j (see Appendix F, Eqs. [F17] to [F25]). If in Eqs. [66] for the components of the spin current density we are allowed to neglect w altogether due to its smallness, then the timelike component j0 spin of the spin current density vanishes and the spacelike part reads jspin ¼ ie 2m ðp À eAÞ Â ðjà sjÞ [68] Figure 6 Interaction of a particle with an external field characterized by the exchange of a photon with three-momentum vector K and angular momentum vector M between the source of the external field (small circle) and the spin particle with initial state c(L1) and final state "cðL2Þ and their associated angular momenta L1 and L2, respectively. VIRTUAL PHOTONS IN MAGNETIC RESONANCE 295 Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a With the three-momentum operator p ¼ Àir we have jspin ¼ e 2m r  ðjà sjÞ À ie2 2m A  ðjà sjÞ [69] Pauli referred to the vector d ¼ jà sj ¼ jà s1j jà s2j jà s3j 0 @ 1 A [70] as spin density vector (Ref. 104, pp. 159–164). In Eqs. [69, 70] we have connected quite diverse objects with different algebraic character. First, d is an ordinary three-vector. In contrast j ¼ (j1, j2)T (the superscript T denotes the transpose), stands for a two-component column vector with wave functions j1 and j2, representing a spinor defined in a two-dimensional Hilbert space and j* ¼ (j1*, j2*) denotes the two-component row vector with conjugate complex elements j1* and j2*, while s1, s2, s3 are operators (given by the Pauli 2Â2 matrices) acting on j. The spin density vector d has the particular feature that any rotation of it in ordinary three-dimensional coordinate space, mediated by the 3Â3 rotation matrix R, is equivalent to a unitary transformation, given by a 2Â2 unitary matrix U in the two-dimensional Hilbert space of spinors j: Rd ¼ Rðjà sjÞ ¼ jà Us1Uþ j jà Us2Uþ j jà Us3Uþ j 0 @ 1 A [71] To separate space (x) and spin (s) variables, we take the ansatz jðx; sÞ ¼ xðxÞtðsÞ with the scalar wave function x(x) depending only on space-time coordinates xm ¼ (ct, r) and the spinor t(s) being a function of spin variables s only. This ansatz is only consistently possible in a nonrelativistic treatment (cf. [26], pp. 134). Thus the nonrelativistic twocomponent spinor wave function is going to be jðx; sÞ ¼ j1 j2   ¼ xðxÞt1ðsÞ xðxÞt2ðsÞ   [72] The functions t1 and t2 are to be regarded as two orthogonal wave functions for the spin-1/2 particle and the scalar function x(x) represents the spatial part of the wave function. For expressions like the spin density vector d ¼ jà sj as in Eqs. [69, 70], we may write d ¼ jà sj ¼ jà s1j jà s2j jà s3j 0 B @ 1 C A ¼ jà 1j2 þ jà 2j1 Àijà 1j2 þ ijà 2j1 jà 1j1 À jà 2j2 0 B @ 1 C A ¼ xà xðtà 1t2 þ tà 2t1Þ Àixà xðtà 1t2 À tà 2t1Þ xà xðtà 1t1 À tà 2t2Þ 0 B @ 1 C A ¼ xà x tT tS tP 0 B @ 1 C A ½73Š Note that in the last equation of [73] we have introduced the spin functions tT, tS, and tP by the definitions tT ¼ tà 1t2 þ tà 2t1; tS ¼ Àiðtà 1t2 À tà 2t1Þ; tP ¼ tà 1t1 À tà 2t2 ½74Š With d being a three-vector with each component being a spin function, it becomes clear that the first term r  ðjà sjÞ in the spin current density jspin (Eq. [69]) is also a vector of functions. The second term A  ðjà sjÞ appearing in jspin contains the three-vector potential A that, when we would take it as field operator and not as an external classical field function, would also cause jspin to become an operator of the electromagnetic field. However as we will see below (Eqs. [76, 77]), we are allowed to disregard the term A  ðjà sjÞ because it does not contribute to the interaction energy of the spin in the electromagnetic field. Thus, finally taking the spin current density as depending only on r  ðjà sjÞ, it represents a vector with functions as components. Therefore, the spin current density fulfills the requirement that we have emphasized in Section ‘‘A QED NMR Probe Model: Pulsed NMR as a Scattering Process,’’ which allowed us to arrive at the formalism of coherent states and quasi-classical states of the electromagnetic field. Spin Operator Formalism Up to and including Eq. [74] we have treated tT, tS, and tP as spinor functions (of spin variables s). In order to find the link to the familiar spin operator formalism commonly used in magnetic resonance, the components tT, tS, and tP appearing in the spin density vector d need to be interpreted as spin operators. This can be rapidly achieved by not relying formally on the spin density vector d but rather directly take the three-vector s ¼ ðs1; s2; s3ÞT of Pauli matrices. It becomes clear that then the resulting spin current density becomes dependent on a spin vector operator s and thus looses its ‘‘innocence’’ of appearing merely as a vector of functions. With this transition from spin wave functions to spin operators, we arrive at 296 ENGELKE Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a ^jspin ¼ e 2m rðxà xÞ Â s À ie2 2m xà xðA  sÞ [75] where now we have written a caret sign over the symbol of the spin current density in order to indicate the formal difference of the function jspin in [69] and the operator ^jspin in [75]. In both cases the spin physics is the same: we are still in the single-particle regime and do not consider quantum field theory of spin-1/2 particles, we just switch from spin functions to the associated spin operators. The only reason to write down the spin current density in the form [75] is to establish the connection to the common spin operator formalism used in magnetic resonance. For the general Hamiltonian density [64], which characterizes the interaction between a Dirac current and external field, we specialize for the spin interaction Hint;spin ¼ e 2m A Á rðxà xÞ Â sÞ À iexà xðA  sÞð ¼ e 2m A Á rðxà xÞ Â sÞð ½76Š where on the right-hand side of the last equation we took into account the identity A Á ðA  sÞ ¼ 0 [77] so the field dependent part of the spin current density does not contribute to the energy of the spin particle in an external field. An alternative derivation of Eq. [76] based on the formalism in k space can be found in Steven Weinberg’s monograph (21). Applying to Eq. [76] a series of transformations using well-known vector relationships (see Appendix F, Eqs. [F26–F35]), we arrive at Hint;spin ¼ e 2m A Á rðxà xÞ Â sð Þ ¼ e 2m xà xB Á t þ r Á ðs  ðxà xAÞÞð Þ ½78Š with the magnetic induction field B as defined by Eq. [F35]. In order to get the Hamiltonian from the Hamiltonian density, we need to integrate over threedimensional space, Hint;spin ¼ Z V d3 xHint;spinðxÞ [79] Applying that to Eq. [78] we obtain Hint;spin ¼ þ e 2m Z V d3 x xà xB Á sð Þ þ e 2m Z V d3 x r Á ðs  ðxà xAÞÞð Þ; ½80Š In [80] we recognize that the divergence term (second term on the right-hand side) can be transformed into a closed surface integral according to Gauss-Ostrogradski’s theorem, i.e., Z V d3 xð ~r Á aÞ ¼ I S dS Á a [81] by setting a ¼ s  ðxà xAÞ, Hint;spin ¼ e 2m Z V d3 x xà xBÁsð Þþ e 2m I S dSÁðsÂðxà xAÞÞ [82] and the surface S encloses the integration volume V. The differential dS is equal to a surface element with associated normal vector dS. Now consider the case of a spin particle strongly localized in three-dimensional space. This means that the probability density x*x in space is a very narrow peak, i.e., in the limit of a point-like particle it is equal to a d function at the coordinate origin if we place the particle there: xà x ¼ 1 2 gd3 ðrÞ; Z V d3 xxà x ¼ 1 [83] g denotes again the Lande´ factor. With the assumption [83] in mind we observe that the surface integral in [82] becomes identically equal to zero, I S dSðs  ðd3 ðrÞAÞÞ ¼ 0 [84] and the volume integral term on the right-hand side of [82] reads Z V d3 x d3 ðrÞB Á s À Á ¼ Bðr ¼ 0Þ Á s ¼ B Á s [85] Hence Hint;spin ¼ gB Á 1 2 s [86] The quantity g ¼ ge 2m [87] is referred to as gyromagnetic ratio. The spin operators s1/2, s2/2, and s3/2 are equal to the components Ix, Iy, and Iz, of the spin vector II: VIRTUAL PHOTONS IN MAGNETIC RESONANCE 297 Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a Ix ¼ 1 2 s1; Iy ¼ 1 2 s2; Iz ¼ 1 2 s3 [88] such that [86] takes the final form of the Zeeman Hamiltonian Hint;spin ¼ gB Á I [89] The Lande´ factor g introduced above in Eq. [83] appears to be slightly larger than 2 for electrons as genuine Dirac particles. As discussed earlier, for nuclei, g cannot be determined this way—Dirac’s theory is not capable to predict nuclear g factors. However, the principal expression [88] and [89] remain valid with the nuclear gyromagnetic ratio [87] obtained either from experiment or from a theory of strong nuclear interactions. Let us return briefly to the classical picture of Larmor precession of the magnetic dipolar moment vector g"hI in a static magnetic field. For the sake of connecting this classical picture with the QED view, consider the following heuristic argument. Take a particle with the intrinsic angular momentum L ¼ "hI [90] with the spin vector operator I ¼ ðIx; Iy; IzÞ according to Eq. [88]. The particle is situated in an external static field aligned along the z axis. According to classical physics the angular momentum vector L will perform a Larmor precession with angular frequency o around the z axis, as illustrated in Fig. 7A. Although during the precession motion the length of L remains constant, the direction of L changes with time. Consider the angular momentum at two successive instants of time separated by the interval Dt. Let L1 ¼ Lðt1Þ and L2 ¼ Lðt1 þ DtÞ and denote the difference vector that arises from this discretized Larmor precession by M ¼ L1 À L2. We just have expressed the conservation of angular momentum for the system particle þ field: the change of angular momentum L2 À L1 during the precession motion of the vector L in the static field is compensated by the angular momentum M conveyed from the particle to the static magnetic field, or vice versa, from the field to the particle, such that M þ ðL2 À L1Þ ¼ 0 [Fig. 7(B,C)]. The interaction energy [89] of the particle does not change during Larmor precession. If we declare a virtual photon as the arbiter of the interaction between the source of the static magnetic field and the spin particle, then this photon carries the angular momentum M ¼ L1 À L2. In addition, this photon possesses the linear momentum K and a nonnegative energy K0. Yet we have to conclude that the energy of this virtual photon is equal to zero, because absorption or emission of the photon just identified by the spin particle with angular momentum L while performing Larmor precession does not change the energy of the spin particle in the static magnetic field. This is also a statement about the certainty of energy in this specific interaction process—certainty of the energy of the spin particle as well as certainty of the photon energy. In other words, because of the condition that the spin particle before and after the emission or absorption event of the virtual photon has the same energy, the virtual photon cannot carry finite energy. The emission or absorption event in Figs. 6 and 7(C) occurs, symbolically, at the vertex where the lines meet, the photon line is associated with K0 ¼ 0 and with the finite angular momentum M as well as linear momentum K (both may be expressed in combination with each other as the helicity operator MÁK/(|M||K|) of the virtual photon. Note, in the argument for the zero energy of the virtual photon involved in Larmor precession we have not included yet any appeal that this photon is off-shell. We just stated that at the interaction vertex [Figs. 6 and 7(c)] the balance of energy, momentum, Figure 7 Conservation of angular momentum during the Larmor precession of an magnetic dipole associated with the spin angular momentum L of a particle in an external static field B. Although the vector L has constant length, its direction changes over time. The resulting angular momentum M is taken from, or conveyed to a virtual photon which mediates the interaction. 298 ENGELKE Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a and angular momentum between incoming particles (here the spin particle) and outgoing particles (again the spin particle and the virtual photon) has to be maintained. This vertex property is universally valid—we will elaborate that in a slightly more general way in Section ‘‘Outlook and Conclusion’’ when discussing Feynman rules and Feynman diagrams. The statement that the virtual photon carries zero energy means that we consider the energy to be certain, i.e., for the uncertainty we have DE ? 0. In Section ‘‘A QED NMR Probe Model: Pulsed NMR as a Scattering Process’’ we have already spoken about the signature of virtual photons. Ascribing the energy K0 ¼ 0 to the photon creates an extreme case for a virtual photon: the zero-mass shell (with radius K0) degenerates to a point in k space and the three-momentum vector K is uncertain, so the photon is really far off-shell. As the uncertainty relation dictates, according to Eq. [35] and as discussed in Section ‘‘A QED NMR Probe Model: Pulsed NMR as a Scattering Process,’’ in the present case we consider the two complementary (i.e., noncommuting) observables energy E and three-momentum K (or energy E and angular momentum M). The characteristic time interval associated to E and K is given by DtK ¼ DK/FK with the force FK equal to the total time derivative of hKi. This leads to the uncertainty relation DEDtK ! "h=2 and for DE ? 0 we have to conclude DtK ? 1, the latter either because DK ? 1 (or because FK ? 0). The situation that the momentum uncertainty DK ? 1 refers to the fact that for virtual photons in static interactions, the sharp energy (zero radius of the zero mass shell) is associated with an completely uncertain momentum K, an extreme case for virtual photons. The heuristic argument for the exchange of virtual photons with zero energy between the spin particle and the surrounding magnet current generating the static induction field is not only appropriate when starting from the classical view with Larmor precession, we may also take the spin-1/2 particle quantummechanically. The spin angular momentum I is quantized along the axis of the magnetic induction field. Let this be defined as the z axis, so that eigenstates of the spin component Iz are simultaneously energy eigenstates of the spin particle in the static field B. There are two such eigenstates for spin-1/2 particles, both states differ in energy (Zeeman levels) by "ho with o being equal to the Larmor frequency. However, the spin particle thus characterized does not perform transitions from one Zeeman state to the other Zeeman state as long as there is no perturbation acting on the spin particle or as long as spontaneous emission does not occur, hence the spin particle does not change its energy. The external perturbation on the spin could, e.g., arise from a time-harmonic field superimposed on the static field or it could originate from relaxation processes. Except for such external perturbations, the spin remains in its Zeeman energy eigenstate, hence its energy does not change. The diagram in Fig. 7(C) has been drawn in such a way to show the similarity to the diagram in Fig. 6, or to the general Feynman diagram in Figs. 1 and 2. In contrast to our discussion in Section ‘‘A QED NMR Probe Model: Pulsed NMR as a Scattering Process’’ where we modeled the interaction between an rf or microwave pulse of short duration with a spin particle as a scattering process, the QED picture of Larmor precession confronts us with a different situation. First, it is not appropriate to view Larmor precession as a short-time scattering process, i.e., assuming that the spin particle is submitted to the static magnetic field only for a limited short time interval. It is rather the opposite, we face a situation where the spin particle is permanently interacting with the external static field, at least for time periods many orders of magnitude larger than the duration of any rf or microwave pulse. Second, it becomes thus clear that the diagram in Fig. 6 can only represent the elementary process, a building block showing the principle of photon exchange during Larmor precession such as in Fig. 7(A) where it becomes obvious that only a small time interval is considered. A more appropriate diagrammatic representation covering the spirit of the whole process of permanent interaction of a spin particle in a constant magnetic field is shown in Fig. 8. It illustrates the repeated exchange of virtual photons between the spin current density [69,75] and the current density of the magnet coil generating the constant magnetic field in which the spin particle is embedded. The Feynman diagram of Fig. 6 can be seen as an element of the extended diagram in Fig. 8. The QED formal treatment of multiple exchange processes as illustrated in Fig. 8 would require to go into the full theory of bound states, i.e., a theory that takes into account not just short scattering events but time-like extended, permanent interactions. Having in mind the introductory character of the present article, this clearly would exceed its scope. INTERACTION OF A SPIN-1/2 PARTICLE WITH EXTERNAL TIME-HARMONIC FIELDS In the model for a magnetic resonance probe introduced in Section ‘‘A QED NMR Probe Model: Pulsed NMR as a Scattering Process’’ we supposedly VIRTUAL PHOTONS IN MAGNETIC RESONANCE 299 Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a dealt with current density functions. We will reexamine this assumption more closely now. In spacetime we do easily distinguish two current densities, j(x) and j(y). The first one, j(x), is related to the rf current where electrons in the conduction band in a metal are the carriers of the current. These conduction-band electrons could be characterized by Bloch wave functions in the periodic potential of a metal lattice or simply approximated as nearly free electrons with the spatial boundary condition that restricts their position distribution to inside the macroscopic metal parts that constitute, e.g., the resonator or coil. The second current density, j(y), relates to the spins in the sample in a different space region. With this distinction, j(x) and j(y) certainly commute, because even when both current densities would be operators, they refer to different particles or different variables—conduction electrons in the coil or circuit on one side, spin particles in the sample on the other side—we consider the two currents as distinguishable. The situation would change if we have a more general situation: we may regard all nearly free electrons in the metal conduction band as indistinguishable among themselves, or likewise, an assembly of identical spin particles represents a statistical ensemble of indistinguishable particles. Therefore, within one family of particles for one specific current density when treating the particles as fermions characterized by wave or field functions and then performing quantization of the fermion field, it is not justified to treat the current density in each family as noncommuting for different space-time points. However, this is not the case that we treat in the present article. In the sequel we will study the interaction between the rf current density j(x) and spin particles under the following circumstances: we are concerned with j(x) as a classical, macroscopic current density and look at the coupling with a single spin. Hence, even with j(x) being a classical function, it generates the quantized electromagnetic field in some coherent state |ai whose time evolution governed by Glauber’s displacement operator Da is given by Eq. [61]. The spin current density j(y), as given by the first term on the right-hand side in Eqs. [69], has vector character with vector components being functions. Hence the condition that the current densities are functions (thus they commute) is satisfied and all the previous theoretical implications for the quantized electromagnetic field apply, as discussed in Section ‘‘A QED NMR Probe Model: Pulsed NMR as a Scattering Process.’’ Turning back to Eq. [52], which expresses the time evolution operator for the electromagnetic field, we look at the exponential expression containing the real part d((xÀy)2 ) of the photon propagator DF(xÀy), and take j(y) as a spin current density function according to Eq. [69]. The electromagnetic field (one mode) is transformed by Da. The exponential expression in [52] depends on the spin current density, it does not affect coherent states |ai. There are spin states |si, these in turn are not affected by Da. As we recognize now, we have achieved a factorization of the timeevolution operator U(t) such that for any matrix element of U(t) formed with product states |a,si ¼ |ai |si it holds ha; sjUðtÞja0 ; s0 i ¼ hajDaðtÞja0 i  hsj exp i 8p Zt À1 dx0 Z d3 x Zt À1 dy0 0 @  Z d3 yjn ðxÞdððx À yÞ2 ÞjnðyÞ  js0 i ½91Š In the derivation of the unitary operator U performed in Section ‘‘A QED NMR Probe Model: Pulsed NMR as a Scattering Process,’’ we relied on Figure 8 A special Feynman diagram illustrating the repeated photon exchange between the magnet static current density j0(x) and the spin current density jspin(y). The space-time points y1, y2, . . . denote time intervals and refer to orientations of the spin angular momentum during Larmor precession. 300 ENGELKE Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a the assumption that, formally, the current densities j(x) and j(y) represent functions. Furthermore, we have shown, beginning with the general Dirac current density as given in Eq. [62], that the spin current density [69] is, indeed, a vector with spin wave functions as components. Furthermore in Section ‘‘Spin Current Density, Zeeman Hamiltonian, and Larmor Precession’’ we have seen that the spin current density function, jspin, Eq. [69], has an associated operator counterpart, ^jspin, Eq. [75]. If we want to include in our arguments not only the time evolution of the electromagnetic field but also the quantum time evolution of the spin-1/2 particle when discussing the unitary operator U, we have to perform the subtle switch from taking j(y) as a function to taking ^jðyÞ (note the caret symbol) as an operator depending on spin operators. We observe that this is an a posteriori construction like in Section ‘‘Spin Current Density, Zeeman Hamiltonian, and Larmor Precession,’’ with the purpose to incorporate the more familiar spin operator formalism. We could live without this construct, in that case the exponential in Eq. [91] inside the Dirac bra hs| and the Dirac ket |s0 i would become simply a complex number and U would describe the time evolution of the electromagnetic field only. With the operator ^jðyÞ for the spin current density the unitary operator for the time evolution of the spin reads VðtÞ ¼ exp i 8p Zt À1 dx0 Z d3 x Zt À1 dy0 0 @  Z d3 yjn ðxÞdððx À yÞ2 Þ^jnðyÞ 1 A ½92Š such that the complete time evolution operator for the electromagnetic field and the spin can be written as UðtÞ ¼ DaðtÞ  VðtÞ [93] The two unitary operators Da and V act on different kinds of state functions, either states of the electromagnetic field or spin states, thus their product in [93] is rather to be understood as direct product, not as an ordinary matrix product. We may summarize the situation as follows: (i) the single-mode electromagnetic field Am evolves according to the unitary transformation [61] with Glauber’s displacement operator Da, where the field parameter a depends on the current density in k space. This part describes the action on the field originating from all the current densities (arising from the rf current as well as the spin current). The photons involved are asymptotically free photons, the ‘‘constituents’’ of the interacting and outgoing rf pulse. (ii) the states |si of the spin particle evolve according to the unitary time evolution V(t)|si with the unitary operator V given by Eq. [92]. Here we have built-in the direct interaction between spin current and rf current density. The photons appearing in V(t) are virtual photons being exchanged between the classical current j(x) and the spin particle current density ^jðyÞ as formally indicated by the d function in the real part of DF(xÀy) inside the integral in Eq. [92]. For the purpose of illustration, let us investigate coherent states |ai with a small number of photons (Fig. 9). First, the ground state of the electromagnetic field is the vacuum state |0i, this is a coherent state and simultaneously it is also a Fock state (with the Figure 9 Poisson probability distributions over numbers n of asymptotically free photons with the electromagnetic field in various coherent states |ai according to Eq. [57] with associated average photon numbers "n ¼ aaà . VIRTUAL PHOTONS IN MAGNETIC RESONANCE 301 Concepts in Magnetic Resonance Part A (Bridging Education and Research) DOI 10.1002/cmr.a lowest possible energy). Only the state |0i can claim that double role. With the field in state |0i the average number "n ¼ 0 and the probability to find exactly zero photons in the field, i.e., n ¼ 0, is equal to unity (Fig. 9, top histogram), hence the probability that there are n . 0 photons is identical to zero. That means that in the vacuum state |0i there are no asymptotically free photons, but virtual photons do occur. Now consider the coherent state |ai with an average photon number "n ¼ aaà ¼ 1. According to Eq. [56], this state is equal to the superposition of Fock states jaðtÞi ¼ h0jaij0i þ h1jaij1i þ h2jaij2i þ . . . so due to the histogram in the second row in Fig. 9, there is a finite probability to find n ¼ 1 or n ¼ 2 or . . . asymptotically free photons, but also there is still a significant probability for n ¼ 0 (the case where only virtual photons, but no asymptotically free photons occur). In that specific coherent state with "n ¼ 1 the probability to have zero asymptotically free (i.e., to find only virtual) photons in the field is equal to the probability to find exactly n ¼ 1 photons in the field. The same argument can be iterated now for coherent states |ai with higher average numbers "n ¼ aaà ¼ 2; 3; . . . where from inspection of the histograms in Fig. 9 for these cases we recognize that the maximum of the probability distribution occurs always for n ¼ "n and the width of the distribution (not shown here, but being equal to the standard deviation) is equal to ffiffiffi "n p . Having thus illustrated the uncertainty of the photon number n in electromagnetic fields being in coherent states (we only know the average and the standard deviation), it becomes obvious that this uncertainty directly relates to the energy of the field—here not to be confused with the energy of a single photon: every asymptotically free photon for a given field mode k carries an energy "ho and is onshell, but the photon number is uncertain, and so is the total electromagnetic field energy being the sum over all photon energies. Specifically the uncertainty of the photon number could be understood as photon emission to the field or photon absorption from the field, hence a varying number of photons over time requiring that the average "n ¼ aaà , now being taken as time average, is sustained and as long as the Poissonian photon distribution is maintained for the field mode considered. In particular, the time evolution operator Da allows photon emission, either from the rf current density or from the spin current density into the rf field. Since in time-harmonic fields oscillating with the angular frequency o each asymptotically free photon carries energy equal to "ho, for a given field mode, each act of emission or absorption of these asymptotically free photons changes the energy of the participating particle whose motion or spin constitutes the respective current density and changes the energy of the field, accordingly. The only exception from this general picture is the vacuum state |0i; insofar here specifically all emissions lead to subsequent complete absorption with the result of net number zero of asymptotically free photons in the field. We want to corroborate the fact that the unitary operator V(t) characterizes the evolution of the spin state as claimed above. For that purpose, let us derive a more familiar form for V(t) explicitly exhibiting the spin operators in the spin current density as defined in Eq. [75]. We introduce the four-potential function as the convolution integral of the classical rf current density j(x) in the coil or resonator and the real part