Vibrational-kinetics methods and their applications to molecular lasers and laser chemistry

Abstract

The vibrational kinetics of molecules simulated by anharmonic oscillators is developed under essentially nonequilibrium conditions. Analytic expressions are obtained for the vibrational distribution function, the relaxation time, and the dependence of the vibrational energy on the pump power; the limiting capacity of the energy reservoir of the anharmonic molecules is estimated. Vibrational kinetics is investigated in mixtures and a redistribution of the vibrational energy among the modes is observed as a function of the component concentration. The singularities of vibrational relaxation in liquids and molecular crystals, due to collective interactions, are studied. A number of concrete applications are considered: the rate of nonequilibrium dissociation is calculated, an analytic model is developed for the CO laser, isotope separation in chemical reactions of vibrationally excited molecules is investigated, and a new type of lasers based on intramolecular transitions in liquids and molecular crystals is proposed.