Density functional response approach for the linear and nonlinear electric properties of molecules

Abstract

This is a preliminary study toward implementation of analytic density functional response approach for molecules to obtain linear and nonlinear electric properties. The Kohn-Sham framework has been used with Gaussian basis sets. We propose a fully variational approach to obtain the response of electronic density in terms of the atomic orbital basis (contracted Gaussians). As a first step, this derivative of the Kohn-Sham operator is obtained by a finite field method using five different values of electric field. Using this, we obtain the energy derivatives up to third order using fully analytic expressions. We calculate the dipole moment, polarizability, and hyperpolarizability of the hydrogen fluoride (HF) molecule as a test case using different exchange-correlation functionals and basis sets within the present methodology. We also explore the feasibility of this response approach by studying the properties of the HF molecule for different H-F distances.