The influence of relativistic effects on nuclear magnetic resonance spin-spin coupling constant polarizabilities of H O , H S , H Se , and H Te.

Relativistic and nonrelativistic calculations have been performed on hydrogen peroxide, dihydrogen disulfide, dihydrogen diselenide, and dihydrogen ditelluride, H X (X = O, S, Se, Te), to investigate the consequences of relativistic effects on their structures as well as their nuclear magnetic resonance (NMR) spin-spin coupling constants and spin-spin coupling constant polarizabilites. The study has been performed using both one-component nonrelativistic and four-component relativistic calculations at the density functional theory (DFT) level with the B3LYP exchange-correlation functional. The calculation of nuclear spin-spin coupling constant polarizabilities has been performed by evaluating the components of the third order tensor, nuclear spin-spin coupling polarizability, using quadratic response theory. From this, the pseudoscalar associated with this tensor has also been calculated. The results show that relativistic corrections become very important for H Se and H Te and hint that a new chiral discrimination technique via NMR spectroscopy might be possible for molecules containing elements like Se or Te. © 2018 Wiley Periodicals, Inc.