Table of Contents
Laser Chemistry
Volume 8, Issue 2-4, Pages 211-234

Infrared Multiphoton Dissociation of CF3CHClF: Primary Dissociation and Secondary Photolysis

1Department of Chemistry, Faculty of Science, The University of Tokyo, Hongo, Tokyo 113, Japan
2The Institute of Physical and Chemical Research, Saitama, Wako 351-01, Japan

Received 6 August 1987; Accepted 10 September 1987

Copyright © 1988 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.


The dissociation yield and branching ratio in CO2 laser-induced infrared multiphoton dissociation (IRMPD) of CF3CHClF were investigated by irradiation at 9R(20) 1078.6 cm−1 under an unfocused irradiation geometry (0.75-2.3 J/cm2) and a mildly focused one (1.2-18 J/cm2). By using a Br2-scavenging technique, it was revealed that the primary dissociation of CF3CHClF proceeded mainly via three-centered HCl molecular elimination and C-Cl bond rupture, with minor contributions of C-C bond rupture and HF molecular elimination at higher fluences. The secondary photolysis of the primarily produced species during the laser pulse to yield CF2 and CClF carbenes depended strongly upon the laser fluence.