Density functional theory study of indirect nuclear spin-spin coupling constants with spin-orbit corrections

• Published in: The Journal of chemical physics Vol. 123; no. 1; p. 014101
• Main Authors: Oprea, Corneliu I, Rinkevicius, Zilvinas, Vahtras, Olav, Agren, Hans, Ruud, Kenneth
• Format: Journal Article
• Language: English
• Published: United States 01.07.2005
• ISSN: 0021-9606
• DOI: 10.1063/1.1947190

This work outlines the calculation of indirect nuclear spin-spin coupling constants with spin-orbit corrections using density functional response theory. The nonrelativistic indirect nuclear spin-spin couplings are evaluated using the linear response method, whereas the relativistic spin-orbit corrections are computed using quadratic response theory. The formalism is applied to the homologous systems H2X (X=O,S,Se,Te) and XH4 (X=C,Si,Ge,Sn,Pb) to calculate the indirect nuclear spin-spin coupling constants between the protons. The results confirm that spin-orbit corrections are important for compounds of the H2X series, for which the electronic structure allows for an efficient coupling between the nuclei mediated by the spin-orbit interaction, whereas in the case of the XH4 series the opposite situation is encountered and the spin-orbit corrections are negligible for all compounds of this series. In addition we analyze the performance of the density functional theory in the calculations of nonrelativistic indirect nuclear spin-spin coupling constants.