Knowledge Bank

The spectroscopy of molecules in condensed systems requires the consideration of the explicit interaction of the solute with its molecular environment, e.g., host lattice or solvent. In this study, kinetic cage effects are brought into a common focus with perturbation ideas on the intramolecular potential for molecular motion as modulated by intermolecular potential contributions. The kinetic inequalities $ke1\gg kvib\gg krelax$ have their analogs in energy term inequalities in the complete Hamiltonian for a molecular solute interaction with the molecular environment. The Born-Oppenheimer separation of very fast and very slow events allows the $Vrelax$ (intermolecular) term to be added to the $Vvib$ (intramolecular) term as a perturbation. The consideration of a series of molecular motions represented by a variety of theoretical potential functions permits a prediction of novel phenomenological consequences of the contribution of $Vrelax$ from the molecule-environment perturbation.