Inquiring ¹⁹⁹Hg NMR Parameters by Combining Ab Initio Molecular Dynamics and Relativistic NMR Calculations

Ab initio molecular dynamics (AIMD) sampling followed by relativistic density functional theory (DFT) ¹⁹⁹Hg NMR calculations were performed for Hg organometallic complexes in water, dimethyl sulfoxide, and chloroform. The spin-orbit coupling, a relativistic effect, is a key factor for predicting δ(Hg) and ¹J(Hg-C) accurately, in conjunction with a dynamic treatment of the systems. Good agreement between the theoretical and experimental results is reached by adopting implicit (based on a continuum model) and explicit (solvent molecules treated quantum mechanically) solvation models. Broader trends appearing in the experimental data available in the literature are reproduced by the calculations, and therefore, quantum chemistry is able to assist in the assignment and interpretation of ¹⁹⁹Hg NMR data. Less pronounced trends, such as changes in the ¹⁹⁹Hg chemical shift in different systems with the same atom types bound to Hg, are too weak to be predicted reliably by the current state-of-the-art theoretical methods based on AIMD sampling and relativistic DFT with hybrid functionals for NMR calculations.