Quantum ergodicity and energy flow in molecules

Abstract

We review a theory for coupled many-nonlinear oscillator systems that describes quantum ergodicity and energy flow in molecules. The theory exploits the isomorphism between quantum energy flow in Fock space, that is, vibrational state space, and single-particle quantum transport in disordered solid-state systems. The quantum ergodicity transition in molecules is thereby analogous to the Anderson transition in disordered solids. The theory reviewed here, local random matrix theory (LRMT), describes the nature of the quantum ergodicity transition, statistical properties of vibrational eigenstates, and quantum energy flow through the vibrational states of molecules. Predictions of LRMT have been observed in computational studies of coupled nonlinear oscillator systems, which are summarized here. We also review applications of LRMT to molecular spectroscopy and chemical reaction rate theory, including adoption of LRMT in theories that predict rates of conformational change of molecules taking place at energies corresponding to those below and above the quantum ergodicity transition. A number of specific examples are reviewed, including the application of LRMT to predict (1) dilution factors of IR spectra of organic molecules, (2) rates of conformational change in chemical and photochemical reactions, (3) conformational dynamics of biological molecules in molecular beams, (4) rates of hydrogen bond breaking and rearrangement in clusters of biological molecules and water, and (5) excited state proton transfer reactions in proteins.