Intensities and dipole moment derivatives of the fundamental bands of 35ClO2 and an intensity analysis of the ν1 band

Abstract

Integrated band intensities of all the fundamental bands of OClO as well as the 2ν1 overtone and the ν1 + ν3 combination band have been measured. Dipole moment derivatives with respect to the normal coordinates have been derived for these bands. For the ν1 band of 35ClO2 individual relative lines intensities have been obtained for many high Ka rR-branch lines, and a systematic deviation from intensities calculated from a zero order model, in which rotation-vibration interactions are not included, has been found. The deviation can be explained with the use of a transformed dipole moment operator. We have compared these results with those obtained using an expression derived by Watson for symmetric tops. Since OClO is a near-prolate symmetric top, dipole transition moments calculated with the two approaches are in good agreement. By reducing the expressions for an asymmetric top to those of the symmetric-top limit, a relationship is found between the parameters of both models which is in good agreement with the coefficients obtained in the data fittings. © 1992 Published by Elsevier Inc.