Properties of random state manifolds with applications to intramolecular vibrational redistribution

The spectral properties of random state manifolds with a bright state coupled to mutually-uncoupled dark states were examined, taking into account the Poisson and Wigner distributions of the energy spacings of the dark states. Density of states (DOS) rearrangement was performed, and the averages of the intensity spectra, the DOS, the dilution factor, Heller's fraction of the occupied phase space, and Perry's effective density of the dark states were determined for the Poisson model. The results are discussed with those of perturbational and Monte Carlo analyses.