Near-Hartree-Fock calculation of the electric field gradients and their first and second derivatives with respect to the bond-length at the location of the deuterium nucleus

Abstract

The electric field gradients and their first and second derivatives with respect to the bond length at the location of the deuterium nucleus are calculated for D₂, DF, DCN, CD₄, CD₃F, CD₃Cl and CD₃NO₂, respectively. These parameters are required for vibration and vibration-rotation coupling corrections to N.M.R. measurements in liquid crystal solvents. A special basis set with local near-Hartree-Fock quality has been constructed which yields very accurate results for the examples where experimental results are available. The results show that at least in some cases the effect of electron correlation has been overestimated.