Ab initio SCF and MP2 calculations of the frequency dependence of the polarizability of cyclohexane

Abstract

The static and dynamic dipole polarizabilities of the cyclohexane molecule are calculated at the SCF level using a basis set optimized for polarizability calculations. MP2 corrections to the static polarizability components are used to obtain approximate MP2 dynamic polarizabilities, which are systematically 5% below the best experimental results. The Rayleigh depolarization ratio is predicted to be independent of frequency, in direct contradiction with experiment, raising questions about the role of the vibrational Raman contribution to the experimental measurements. Further observations at lower frequencies are recommended.