Level-dependent damping in intermolecular vibrations: Linear spectroscopy

A treatment of stimulated Raman intermolecular spectroscopy is presented that employs a Landau–Teller model of damping. This model incorporates a quantum-number dependence to population relaxation and pure dephasing, thereby introducing a specific temperature and frequency dependence into the damping in the intermolecular spectrum. Optical-heterodyne detected Raman-induced Kerr effect data obtained in CS2 and acetonitrile over a broad temperature range are shown to agree with the basic predictions of the model.