Vibrational intensities in methane

Abstract

The absorption intensities of the two infra-red active vibrations in methane have been obtained from a perturbation calculation on the equilibrium wave functions derived in the preceding paper. The perturbation field is the change in the potential field due to the nuclei which results from moving the nuclei in the vibrational coordinate concerned, and a simplified form of second order perturbation theory, developed by Pople and Schofield, is used for the calculation. The main approximation involved is the neglect of f and higher harmonics in the spherical harmonic expansion of the nuclear field. The resulting dipole moment derivatives are approximately three times larger than the experimental values, but they show qualitative features and sign relationships which are significant. The experimental intensity measurements are interpreted and discussed in relation to these results.