C9550 Advanced Quantum Chemistry and Molecular Spectroscopy

Faculty of Science
Autumn 2018
Extent and Intensity
2/0/0. 2 credit(s) (fasci plus compl plus > 4). Type of Completion: zk (examination).
Teacher(s)
doc. Mgr. Markéta Munzarová, Dr. rer. nat. (lecturer)
Cina Foroutannejad, Ph.D. (assistant)
Guaranteed by
doc. Mgr. Markéta Munzarová, Dr. rer. nat.
Department of Chemistry – Chemistry Section – Faculty of Science
Contact Person: doc. Mgr. Markéta Munzarová, Dr. rer. nat.
Supplier department: Department of Chemistry – Chemistry Section – Faculty of Science
Prerequisites
Absolving of course C9920.
Course Enrolment Limitations
The course is also offered to the students of the fields other than those the course is directly associated with.
fields of study / plans the course is directly associated with
Course objectives
The goal of the course is to explain to students relationships between molecular geometric and electronic structure and spectroscopical parameters of molecules.
Learning outcomes
At the end of the course, students will understand relationships between molecular structure (geometric as well as electronic) and molecular spectroscopy parameters. They will be able to interpret simple spectra rotational, vibrational, electronic and magnetic resonance ones.
Syllabus
  • 1. Principles of molecular spectroscopy 1.1 Introduction 1.1.1 The meaning of the notion "spectroscopy" 1.1.2. Emission, absorption, stimulated emission, dispersion of the radiation. The electromagnetic spectrum and the kinds of molecular excitations. The components of a spectrometer: The sources of radiation, monochromators: prisms, diffraction gratings, detectors. 2. The width and intensity of the lines. Spectral resolution. The influences on spectral resolution: natural line width, Doppler broadening, pressure broadening, means of influencing line width in a spectrum. Line intensity: Level populations for spontaneous emission, absorption, stimulated emission. Stationary state. Line intensity for absorption in various spectral regions. 3. Postulates of the quantum mechanics. The wavefunction postulate. The postulate about operators. The postulate about the expectation value of a measurement. The postulate about the time-dependent Schrödinger equation. Stationary Schrödinger equation. 4. Exact solutions of the Schrödinger equation I. Particle in a one-dimensional potential well and electronic structure of conjugated hydrocarbons. Particle on a circle. Particle on a sphere. Particle in a Coulomb field. 5. Exact solutions of the Schrödinger equation II. The harmonic oscillator. Harmonic oscillator in a classical mechanics. Quantum-mechanical Hamiltonian. The Schrödinger equation for the harmonic oscillator. Solution in a coordinate representation. The principle of recursion formulas. Eigenfunctions and eigenvalues. 6. Approximate solutions of the Schrödinger equation: The time-dependent perturbation theory. The form of the wavefunction as a combination of ground and excited states, probability of transition in the case of periodic perturbation, the meaning of the notion transition moment. The principle of the selection rules. 7. Rotational spectra. Rotation levels of energy, the classification of rotators. Free linear rotor: rigid rotor – energy levels and eigenfunctions, rotational constant, selection rules. Line intensities. Applications of microwave spectroscopy. Stark effect. Non-rigid rotor. Spherical rotor. Symmetrical rotor. 8. Vibrational spectra. Diatomic molecules: Anharmonic oscillator, Morse potential. Approximate solution of the Schrödinger equation with the Morse potential. Fundamental frequencies and vibrational overtones. Anharmonic oscillator-rotor. Vibrational spectra of polyatomic molecules: the calculation of vibrational frequencies for CO2: the formulation of the problem, the resulting set of equations, resulting frequencies. General description of vibration. Selection rules: infrared spectra and Raman spectra. Fourier transformed infrared spectra. 9. Electronic spectra. Born-Oppenheimer approximation and the form of the wavefunction in this approximation. Franck-Condon principle (selection rules for electronic transitions). Line intensity as a function of overlap between electronic functions of ground and excited states. Electronic spectra of polyatomic molecules. 10. Photoelectron and related spectroscopies. The principle of photoelectron spectroscopy. Photoelectron spectroscopy on atoms. Photoelectron spectroscopy on molecules. Roentgenfluorescence spectroscopy. 11. Electron Paramagnetic Resonance (EPR). Operators and eigenfunctions of spin. Spins in magnetic field. Transitions between eigenstates. Techniques for mapping the transitions between eigenstates. Energy levels in the presence of a magnetic field, unpaired electron and magnetic nucleus. The g-factor and the hyperfine splitting. The notion of spin density and spin population. Relationships between structure and hyperfine splitting for organic radicals and transition metal complexes. 12. Nuclear Magnetic Resonance (NMR). Foundations. Energy eigenvalues and selection rules. Classical description of NMR. High resolution NMR in liquids. The influence of dynamical effects on NMR spectra. NMR pulsed Fourier-transformed spectroscopy.
Literature
    recommended literature
  • HOLLAS, J. Michael. Modern spectroscopy. 4th ed. Hoboken, N.J.: John Wiley & Sons, 2004, xxvii, 452. ISBN 0470844167. URL info
  • ATKINS, P. W. and R. S. FRIEDMAN. Molecular quantum mechanics. 5th ed. New York: Oxford University Press, 2011, xiv, 537. ISBN 9780199541423. info
    not specified
  • CELÝ, Jan. Základy kvantové mechaniky pro chemiky. Vyd. 1. Brno: Rektorát UJEP, 1983, 161 s. info
  • LEVINE, Ira N. Molecular spectroscopy. New York: John Wiley & Sons, 1975, x, 491. ISBN 0471531286. info
Teaching methods
Lectures and exercises "in one". Students take actively part on solving selected tasks at the whiteboard.
Assessment methods
Written exam - test followed by an oral exam. Of total 40 points, 20 must be gained for successful absolving of the course.
Language of instruction
Czech
Follow-Up Courses
Further comments (probably available only in Czech)
Study Materials
The course is taught annually.
The course is taught: every week.
Teacher's information
http://www.chemi.muni.cz/nmr/radek/C9950/index.html
The course is also listed under the following terms Autumn 2007 - for the purpose of the accreditation, Autumn 2010 - only for the accreditation, Autumn 2009, Autumn 2010, Autumn 2011, Autumn 2011 - acreditation, Autumn 2013, Autumn 2014, Autumn 2015, Autumn 2016, autumn 2017, Autumn 2019, Autumn 2020, autumn 2021, Autumn 2022, Autumn 2023, Autumn 2024.
  • Enrolment Statistics (Autumn 2018, recent)
  • Permalink: https://is.muni.cz/course/sci/autumn2018/C9550