Through-space spin–spin coupling constants involving fluorine: benchmarking DFT functionals

ABSTRACT

Through-space spin–spin coupling constants (SSCCs) involving fluorine are computed applying Density Functional Theory and compared with experimental data to benchmark the performance of various functionals. In addition to the most often analysed J(FF) constants, we consider examples of J(FN), J(FP), J(FC) and J(FSe) constants. Basis sets optimised for the study of SSCCs are applied and thus we find the choice of the functional to be more important than the choice of the basis set. Different performance of DFT functionals is observed for different SSCCs, with the hybrid DFT functionals generally superior for the through-space couplings. When all the SSCCs are considered, PBE0 appears to be the most robust functional.

GRAPHICAL ABSTRACT

Keywords:

• NMR
• through-space coupling constants
• DFT

Acknowledgments

We dedicate this paper to the memory of the late Professor Dr. Dieter Cremer, who was also one of the pioneers of DFT calculations of NMR spin-spin coupling constants. In particular, his approaches for the analysis in terms of molecular orbitals of the different contributions to the coupling constants have contributed profoundly to the understanding of these important molecular properties.

Disclosure statement

No potential conflict of interest was reported by the authors.

ORCID

Michał Jaszuński http://orcid.org/0000-0003-3982-4683

Paweł Świder http://orcid.org/0000-0002-8306-045X

Stephan P. A. Sauer http://orcid.org/0000-0003-4812-0522

Additional information

Funding

M.J. and P.Ś. acknowledge the support by the National Science Centre (Poland) grant number 2016/21/B/ST4/03904. S.P.A.S. acknowledges support from the Danish Center for Scientific Computing.