Intramolecular Vibrational Redistribution and Unimolecular Reaction: Concepts and New Results on the Femtosecond Dynamics And Statistics in CHBrClF

摘要

We present the conceptual background for intramolecular vibrational (rotational) redistribution (IVR) in polyatomic molecules and its analysis from high resolution spectra. We illustrate some of the basic concepts relating to the use of effective and real molecular hamiltonians for IVR with examples drawn from our previous spectroscopic investigations of the chiral molecule CHFClBr. The importance of the initial state for the dynamics is shown, demonstrating that simple intuitive concepts of survival probabilities or some arbitrary chromophore ("zero order bright") state are insufficient for a quantitative understanding of IVR.