Local group modes and the dynamics of intramolecular energy transfer across a heavy atom

Abstract

The dynamics of energy transfer is discussed for a model system in which two ligands are separated by a heavy atom. Numerical and analytical results are given for the case that each ligand is a CC. In the quasiperiodic regime, the dynamics are interpreted using perturbation theory. Local group modes involved in an intramolecular energy localization which can occur in this regime are identified. An approximate separation of the primarily ligand–ligand motions from the primarily ligand–metal–ligand ones occurs in the clearly quasiperiodic regime and also at an energy where the power spectra of the bond coordinates are "grassy." The overall analysis is used to make predictions for systems with larger ligands, when the primarily metal atom–ligand modes are, as above, approximately separable from the primarily intraligand ones.