The influence of relativistic effects on nuclear magnetic resonance spin–spin coupling constant polarizabilities of H2O2, H2S2, H2Se2, and H2Te2

LARSEN, MARTIN A. B.; FERRARO, MARTA; PAGOLA, GABRIEL I.; SAUER, STEPHAN P. A.

JOURNAL OF COMPUTATIONAL CHEMISTRY

JOHN WILEY & SONS INC

Lugar: Hoboken, New Jersey; Año: 2018 vol. 39 p. 2589 - 2600

0192-8651

Relativistic and nonrelativistic calculations have been performed on hydrogen peroxide, dihydrogen disulfide, dihydrogen diselenide, and dihydrogen ditelluride, H2X2 (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 H2Se2 and H2Te2 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.