Theoretical Calculations of Dipole Moments, Polarizabilities, and Hyperpolarizabilities of HF, OCS, O3, CH3F, and CH3Cl by Local Density Approximation

Abstract

AbstractThe dipole moments, polarizabilities, and hyperpolarizabilities of five molecules (HF, OCS, O3, CH3F, and CH3Cl) have been computed at their experimental equilibrium geometries using the deMon density functional program. For molecules of such sizes, we augmented the basis set of valence double‐zeta plus polarization functions with field‐induced polarization functions. Contamination of least‐squares fitted parameters by higher‐order hyperpolarizabilities have been greatly reduced by fitting the field‐dependent dipole moments to eighth order polynomials using as many as 37 points per molecule. The results compare well with experiment.