Vibrational contributions to nonlinear optical properties of methanol, ethanol and propanol

Abstract

Static and dynamic vibrational contributions to the linear polarizability and the first and second nonlinear hyperpolarizabilities of methanol, ethanol and propanol have been calculated. Both the pure vibrational contribution and the zero-point vibrational averaging contribution have been determined by adopting the perturbation treatment of Bishop and Kirtman at the Hartree–Fock level. The pure vibrational contribution is quite important at the static limit, while in the optical region it varies for different nonlinear optical processes. The zero-point vibrational averaging contribution is a quite large correction to the electronic nonlinear optical (NLO) properties, especially for the second hyperpolarizability at finite fundamental frequencies. Vibrational analysis shows that the swinging modes at around 300 cm −1 and the C–H stretching modes at around 3160 cm −1 often give large contributions.