Fluorine spin-spin coupling constants of pentafluorobenzene revisited at the ab initio correlated levels

Stepan A Ukhanev; Sergei V Fedorov; Yuriy Y Rusakov; Irina L Rusakova; Leonid B Krivdin

doi:10.1002/mrc.5276

Fluorine spin-spin coupling constants of pentafluorobenzene revisited at the ab initio correlated levels

Magn Reson Chem. 2022 Sep;60(9):901-914. doi: 10.1002/mrc.5276. Epub 2022 May 2.

Authors

Stepan A Ukhanev¹, Sergei V Fedorov¹, Yuriy Y Rusakov¹, Irina L Rusakova¹, Leonid B Krivdin¹

Affiliation

¹ A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Irkutsk, Russia.

PMID: 35470458
DOI: 10.1002/mrc.5276

Abstract

All possible spin-spin coupling constants, ¹⁹ F-¹⁹ F, ¹⁹ F-¹³ C, and ¹⁹ F-¹ H, of pentafluorobenzene were calculated at five different levels of theory, HF, DFT, SOPPA (CCSD), CCSD, and the SOPPA (CCSD)-based composite scheme with taking into account solvent, vibrational, relativistic, and correlation corrections. Most corrections were next to negligible for the long-range couplings but quite essential for the one-bond carbon-fluorine coupling constants. Hartree-Fock calculations were found to be entirely unreliable, while DFT results were comparable in accuracy with the data obtained using the wave function-based methods.

Keywords: CCSD; DFT; HF; SOPPA (CCSD); computational 19F NMR; fluorine spin-spin coupling constants; pentafluorobenzene.

Publication types

Letter

MeSH terms

Carbon* / chemistry
Fluorine* / chemistry
Solvents

Substances

Solvents
Fluorine
Carbon