Linking Spin-Orbit NMR Shielding at the Ligh Atom with Magnetically Induced Currents on
                                    Heavy-Atom–Light-Atom Bond


                        Ben Joseph R. Cuyacot, Jan Novotný, and Radek Marek


            Department of Chemistry, Faculty of Science and CEITEC, Masaryk University,

                                Kamenice 5, CZ-62500, Brno, Czechia

                                  benjoseph.cuyacot@mail.muni.cz



            The modulations of NMR shifts of Light Atoms (LA) by the relativistic spin-orbit (SO)
coupling which originates from the neighboring Heavy Atom (HA) have been explored in numerous
theoretical studies.^1-3 This effect was also shown to be significantly influenced by the character
of the HA–LA bond which could be modified by substituents oriented trans to the LA spectator atom.

            In this study we explore the SO HALA effect further by examining the link between the
SO effects on NMR shielding of the light atom (δ^SO) and molecular magnetically induced currents
(SO-MICs).


                                             Picture1


            We used four-component approach employing Dirac–Kohn–Sham Hamiltonian to treat the SO
effects, PBE0 functional, and simple HALA systems. We focused on the currents on HA–LA bonds and in
the vicinity of light atom. The results revealed a clear link between the two properties and
provide additional information about the HA–LA bonds.



REFERENCES

(1)      Novotný, J.; Vícha, J.; Bora, P. L.; Repisky, M.; Straka, M.; Komorovsky, S.; Marek, R. J.
Chem. Theory Comput. 2017, 13 (8), 3586–3601. https://doi.org/10.1021/acs.jctc.7b00444.

(2)      Vícha, J.; Straka, M.; Munzarová, M. L.; Marek, R.. J. Chem. Theory Comput. 2014, 10 (4),
1489–1499.

(3)      Vı́cha, J.; Novotný, J.; Komorovsky, S.; Straka, M.; Kaupp, M.; Marek, R. Chem. Rev. 2020,
120 (15), 7065–7103.