Table of Contents
Laser Chemistry
Volume 7, Issue 1, Pages 1-27

Kinetics of Nonequilibrium Gas Phase Reactions Induced by Vibrational Multiple-Photon IR Laser Excitation of Molecules

1Laser Chemistry Laboratory, Research Centre for Laser Technology, Acad. Sci. USSR, Moscow District, Troitzk 142092, Russia
2Institute of Spectroscopy, Acad. Sci. USSR, Moscow District, Troitzk 142092, Russia

Copyright © 1987 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.


A simple theoretical model for the qualitative description of the kinetics of the unimolecular decay in the pulsed IR laser field with strong deviation from thermal equilibrium is developed. The nonequilibrium character of the reaction is introduced by means of a special parameter of “truncation” of vibrational energy distribution function, which takes into account depletion of the distribution function due to the dissociation. The derived self-consistent system of differential equations describes the three dissociation regimes. Besides, the apparent cases of collisionless (short duration of laser pulse τp) and equilibrium (long τp) reactions, the intermediate collisional-nonequilibrium dissociation is revealed. The contribution of postpulse reaction has proved considerable in case of both long and short pulses. For the case of a successive dissociation the possibility of synthesis of labile products which cannot be produced at thermal initiation is established.