Relativistic nuclear magnetic resonance J-coupling with ultrasoft pseudopotentials and the zeroth-order regular approximation.

Journal article

We present a method for the first-principles calculation of nuclear magnetic resonance (NMR) J-coupling in extended systems using state-of-the-art ultrasoft pseudopotentials and including scalar-relativistic effects. The use of ultrasoft pseudopotentials is allowed by extending the projector augmented wave (PAW) method of Joyce et al. [J. Chem. Phys. 127, 204107 (2007)]. We benchmark it against existing local-orbital quantum chemical calculations and experiments for small molecules containing light elements, with good agreement. Scalar-relativistic effects are included at the zeroth-order regular approximation level of theory and benchmarked against existing local-orbital quantum chemical calculations and experiments for a number of small molecules containing the heavy row six elements W, Pt, Hg, Tl, and Pb, with good agreement. Finally, (1)J(P-Ag) and (2)J(P-Ag-P) couplings are calculated in some larger molecular crystals and compared against solid-state NMR experiments. Some remarks are also made as to improving the numerical stability of dipole perturbations using PAW.

Authors: Green, T; Yates, JR

• Publication status: Published
• Publisher: American Institute of Physics Inc.
• Journal: Journal of chemical physics
• Volume: 140
• Issue: 23
• Pages: 234106
• Publication date: 2014-06-01
• DOI: 10.1063/1.4882678
• EISSN: 1089-7690
• ISSN: 0021-9606
• Language: English