Density-Functional-Based Determination of Vibrational Polarizabilities in Molecules

Abstract

We develop a direct derivation for the primary contribution to the vibrational polarizability for molecules, clusters and other finite systems. The vibrational polarizability is then calculated within the generalized gradient approximation to the density functional theory for a variety of molecules and clusters. The agreement between theory and experiment is quite good. The results show that for small ionic molecules and clusters, inclusion of the vibrational polarizability is necessary to achieve quantitative accuracy.