Vibrational effects on the dynamic electric properties of hydrogen peroxide.

In this work we present a method based on the perturbation theoretic approach of Bishop and co-workers [J. Chem. Phys. 95, 2646 (1991); 97, 5255 (1992); 108, 10013 (1998)] to calculate the effect of torsional motion on the polarizability and hyperpolarizabilities of hydrogen peroxide. The frequency dependence has been evaluated using the time-dependent Hartree-Fock method. The results obtained show that the zero-point vibrational averaging contributions are small compared to the corresponding electronic contributions. In the static limit the pure vibrational contributions are very large, specially for beta and gamma. These contributions are significant for the hyperpolarizabilities even in the visible region, except for the second harmonic generation and third harmonic generation processes.