Estimation of the contribution of vibronic interaction to the isotope effect on the nuclear magnetic shielding constant of a hydrogen bridge

Abstract

A nonadiabatic correction to the H/D isotope effect on the constant of electronic magnetic shielding of a nucleus was estimated within the framework of the first-order perturbation theory. The procedure consists in the ab initio calculation of frequencies and relative intensities in the vibronic spectrum for H and D forms of a molecule taking into account only the transitions allowed in the magnetic-dipole approximation. With the elementary assumptions (case of Herzberg vibronic interaction), the semiquantitative estimation of adiabatic (geometrical) and nonadiabatic contributions to the H/D isotope effect on the 15N shielding constant of a complex with the HF-pyridine hydrogen bond was carried out. These two contributions to the isotope effect are comparable in the order of magnitude, at least for unsaturated molecules with low-lying excited electronic states. A correct solution to the problem requires ab initio calculation that is not based on the Born-Oppenheimer approximation.