Choice of exchange-correlation functional for computing NMR indirect spin-spin coupling constants.

Keal, T.W.; Helgaker, T.; Salek, P.; Tozer, D.J.

Abstract

The choice of exchange-correlation functional for the determination of indirect nuclear spin–spin coupling constants in density-functional theory is considered. In an assessment of one-bond 1JCH couplings, the PBE functional was recently shown [S.N. Maximoff, J.E. Peralta, V. Barone, G.E. Scuseria, J. Chem. Theory Comput. 1 (2005) 541] to perform well, significantly outperforming B3LYP. For couplings involving N, O, and F atoms in simple molecules, we demonstrate that the opposite is observed; PBE is considerably less accurate than B3LYP. By contrast, the B97-2 and B97-3 semi-empirical functionals provide good, consistent quality couplings for all these atom types in an extensive assessment.

Citation

Keal, T., Helgaker, T., Salek, P., & Tozer, D. (2006). Choice of exchange-correlation functional for computing NMR indirect spin-spin coupling constants. Chemical Physics Letters, 425(1-3), 163-166. https://doi.org/10.1016/j.cplett.2006.05.032

• Journal Article Type: Article
• Online Publication Date: May 13, 2006
• Publication Date: 2006-07
• Journal: Chemical Physics Letters
• Print ISSN: 0009-2614
• Publisher: Elsevier
• Peer Reviewed: Peer Reviewed
• Volume: 425
• Issue: 1-3
• Pages: 163-166
• DOI: https://doi.org/10.1016/j.cplett.2006.05.032