The importance of current contributions to shielding constants in density-functional theory

Abstract

The sources of error in the calculation of nuclear-magnetic-resonance shielding constants determined by density-functional theory are examined. Highly accurate Kohn–Sham wave functions are obtained from coupled-cluster electron density functions and used to define accurate—but current independent—density-functional shielding constants. These new reference values, in tandem with high-accuracy coupled-cluster shielding constants, provide a benchmark for the assessment of errors in common density-functional approximations. In particular the role of errors arising in the diamagnetic and paramagnetic terms is investigated, with particular emphasis on the role of current-dependence in the latter. For carbon and nitrogen the current correction is found to be, in some cases, larger than 10 ppm. This indicates that the absence of this correction in general purpose exchange–correlation functionals is one of the main sources of error in shielding calculations using density functional theory. It is shown that the current correction improves the shielding performance of many popular approximate DFT functionals.