The time dependence of spontaneous emission from isolated, highly vibrationally excited molecules is studied from the point of view of the classical and semiclassical mechanics of dissipatively perturbed Hamiltonian systems. A correlation function expression for the time‐dependent emission spectrum serves as a starting point for quasiclassical approximations. These in turn lead to an investigation of the classical dynamics of model molecular systems in which small, energy‐nonconserving terms have been added to Hamilton’s equations. Numerical calculations show rich dynamical behavior which can be qualitatively understood in terms of the resonance structure of the unperturbed system. For example, trajectories tend to be captured by zones of nonlinear resonance. This ‘‘mode locking’’ produces a characteristic cleanup of an emission spectrum that otherwise is rather congested at these energies. The close connection between spectra and dynamics suggests that the classical dynamics of dissipatively perturbed systems may provide a useful language for interpreting radiative and condensed‐phase vibrational relaxation, and possibly some types of intramolecular relaxation phenomena as well.

%B J. Chem. Phys. %V 85 %P 2581 %G eng %U http://dx.doi.org/10.1063/1.451065 %R 10.1063/1.451065