Article
Semiclassical theory of unimolecular dissociation induced by a laser field
The Journal of Chemical Physics
(1978)
Abstract
· A semiclassical nonperturbative theory of direct photodissociation in a laser field is developed in which photon absorption and dissociation are treated in a unified fashion. This is achieved by visualizing nuclear dynamics as a representative particle moving on electronic‐field surfaces. Methods are described for calculating dissociation rates and probabilities by Monte Carlo selection of initial conditions and integration of classical trajectories on these surfaces. This unified theoryreduces to the golden rule expression in the weak‐field and short‐time limits, and predicts nonlinear behavior, i.e., breakdown of the golden rule expression in intense fields. Field strenghts above which lowest‐order perturbation theory fails to work have been estimated for some systems. Useful physical insights provided by the electronic‐field representation have been illustrated. Intense field effects are discussed which are amenable to experimental observation. The semiclassical methods used here are also applicable to multiple‐surface dynamics in fieldfree unimolecular and bimolecular reactions.
Keywords
- • Bimolecular reactions,
- Semiclassical methods,
- Perturbation theory,
- Semiclassical theories,
- Surface dynamics,
- Photodissociation
Disciplines
Publication Date
1978
DOI
10.1063/1.436170
Citation Information
Jian-Min Yuan and Thomas F George. "Semiclassical theory of unimolecular dissociation induced by a laser field" The Journal of Chemical Physics Vol. 68 Iss. 7 (1978) Available at: http://works.bepress.com/thomas-george/260/