Electronic density response to molecular geometric changes from explicit electronic susceptibility calculations

Abstract

We present a first principles approach to compute the response of the molecular electronic charge distribution to a geometric distortion. The scheme is based on an explicit representation of the linear electronic susceptibility. The linear electronic susceptibility is a tensor quantity which directly links the first-order electronic response density to the perturbation potential, without requiring self-consistency. We first show that the electronic susceptibility is almost invariant to small changes in the molecular geometry. We then compute the dipole moments from the response density induced by the geometrical changes. We verify the accuracy by comparing the results to the corresponding values obtained from the self-consistent calculations of the ground-state densities in both geometries.