Jakubowska Katarzyna, Pecul Magdalena, Ruud Kenneth
Faculty of Chemistry, University of Warsaw, 02-093 Warsaw, Poland.
Hylleraas Centre for Quantum Molecular Sciences, Department of Chemistry, UiT─The Arctic University of Norway, N-9037 Tromsø, Norway.
J Phys Chem A. 2022 Oct 6;126(39):7013-7020. doi: 10.1021/acs.jpca.2c05019. Epub 2022 Sep 22.
Zero-point vibrational (ZPV) corrections to the nuclear spin-spin coupling constants have been calculated using four-component Dirac-Kohn-Sham DFT for HX (where X = O, S, Se, Te, Po), XH (where X = N, P, As, Sb, Bi), and XH (where X = C, Si, Ge, Sn, and Pb) molecules and for HC≡CPbH. The main goal was to study the influence of relativistic effects on the ZPV corrections and thus results calculated at relativistic and nonrelativistic approaches have been compared. The effects of relativity become notable for the ZPV corrections to the spin-spin coupling constants for compounds with lighter elements (selenium and germanium) than for the spin-spin coupling constants themselves. In the case of molecules containing heavier atoms, for instance BiH and PbH, relativistic effects play a crucial role on the results and approximating ZPV corrections by the nonrelativistic results may lead to larger errors than omitting ZPV corrections altogether.
已使用四分量狄拉克 - 科恩 - 沙姆密度泛函理论（DFT）对HX（其中X = O、S、Se、Te、Po）、XH（其中X = N、P、As、Sb、Bi）以及XH（其中X = C、Si、Ge、Sn和Pb）分子和HC≡CPbH计算了核自旋 - 自旋耦合常数的零点振动（ZPV）校正。主要目的是研究相对论效应对ZPV校正的影响，因此比较了相对论和非相对论方法计算的结果。对于比自旋 - 自旋耦合常数本身含有更轻元素（硒和锗）的化合物，相对论效应在ZPV校正方面变得显著。在含有较重原子的分子中，例如BiH和PbH，相对论效应在结果中起着关键作用，用非相对论结果近似ZPV校正可能导致比完全忽略ZPV校正更大的误差。
