Fluorescence of supercooled molecules as a probe for intramolecular vibrational redistribution rates

摘要: A theory is developed for the fluorescence spectra of supercooled polyatomic molecules in a jet. single molecular mode (the ’’system’’) assumed to be optically active and other modes constitute ’’bath’’ which induces line broadening relaxation. Since bath finite initially cold, its motion strongly correlated with that system. The reduced dynamics system treated using Mori projection operator technique. present ’’tetradic description’’ becomes useful especially large statistical where many states are involved fluorescence. This precisely limit effective Hamiltonian formalism commonly used intramolecular intermediate size very tedious impractical. may interpreted terms simple rate equations directly monitor vibrational redistribution energy (IVR). We further compare predicted existing experimental results supersonic beams.