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

The 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.