Nuclear magnetic resonance spin–spin coupling constants from coupled perturbed density functional theory

Abstract

For the first time, a complete implementation of coupled perturbed density functional theory (CPDFT) for the calculation of NMR spin–spin coupling constants (SSCCs) with pure and hybrid DFT is presented. By applying this method to several hydrides, hydrocarbons, and molecules with multiple bonds, the performance of DFT for the calculation of SSCCs is analyzed in dependence of the XC functional used. The importance of electron correlation effects is demonstrated and it is shown that the hybrid functional B3LYP leads to the best accuracy of calculated SSCCs. Also, CPDFT is compared with sum-over-states (SOS) DFT where it turns out that the former method is superior to the latter because it explicitly considers the dependence of the Kohn–Sham operator on the perturbed orbitals in DFT when calculating SSCCs. The four different coupling mechanisms contributing to the SSCC are discussed in connection with the electronic structure of the molecule.