Table of Contents
Laser Chemistry
Volume 19 (1999), Issue 1-4, Pages 305-309
http://dx.doi.org/10.1155/1999/98304

Investigating the Environment-dependent Photophysics of Chlorine Dioxide With Resonance Raman Intensities

Dept. of Chemistry, University of Washington, Seattle 98195, WA, USA

Received 7 April 1997

Copyright © 1999 Hindawi Publishing Corporation. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

The condensed-phase excited-state reaction dynamics of chlorine dioxide are investigated using resonance Raman intensity analysis. Absolute Raman intensities are measured on resonance with the 2B22A2 electronic transition and used to establish the excited-state structural evolution which occurs on the 2A2 surface following photoexcitation. Analysis of the intensities demonstrates that excited-state relaxation occurs along all three normal coordinates; however, only modest evolution is observed along the asymmetric stretch. This limited relaxation stands in contrast to the extensive motion along this coordinate in the gas phase. It is proposed that the initial excited-state structural relaxation serves to define the symmetry of the reaction coordinate and thus the mechanism of Cl production following photolysis of OClO.