Intramolecular vibrational energy redistribution in the highly excited fluoroform molecule: a quantum mechanical study using the multiconfiguration time-dependent Hartree algorithm.

Abstract

The present paper is devoted to a detailed study of the intramolecular vibrational energy redistribution in fluoroform initiated by a local mode excitation of the CH stretch [nnu(CH) (n=1,...,4)]. All nine internal degrees of freedom are explicitly taken into account and the full quantum mechanical simulation is performed by means of the multiconfiguration time-dependent Hartree algorithm. The existence of different time scales considerably complicates the dynamics. The mode-to-mode energy transfer is analyzed by calculating the evolution of the partial energies of all vibrational modes. This study emphasizes the crucial role played by the two-dimensional FCH bending modes which act as an energy reservoir. The fast energy flow into these bending modes significantly hinders an energy flow from the CH chromophore. Finally, our results are compared with those obtained previously with the wave operator sorting algorithm approach.