An ab initio study of vibrational corrections to the electrical properties of ethane

Abstract

SCF quartic property hypersurfaces have been computed for the energy, quadrupole moment and polarizability tensor of ethane via finite differences of analytical derivatives to obtain zeropoint vibrational corrections to the properties. Coupled with accurate electrical properties computed at a correlated r e geometry, using a range of correlated methods, especially BD and BD(T), excellent estimates of these properties have been obtained that incorporate the effects of vibrational averaging. The effect of deuterium substitution on the properties has been investigated, including the first known theoretical prediction of the dipole moment of CH3CD3, and the frequency dependence of the polarizability tensor and Rayleigh depolarization ratio have been examined. Careful attention has been paid to a critical comparison between these theoretical estimates and experimental measurements. Although the vibrational corrections are limited to SCF theory, and basis sets not as extensive as used in some studies of this kind, nevertheless the results can be compared quantitatively with experiment, and the agreement is found to be excellent. The results underline the necessity to allow for the effects of zero-point vibrational averaging when comparing theory with experiment, and suggest a viable approach for studies on larger molecules.