The vibrational energy flow transition in organic molecules: Theory meets experiment

R. Bigwood, M. Gruebele, D. M. Leitner, P. G. Wolynes

Research output: Contribution to journalArticlepeer-review


Most large dynamical systems are thought to have ergodic dynamics, whereas small systems may not have free interchange of energy between degrees of freedom. This assumption is made in many areas of chemistry and physics, ranging from nuclei to reacting molecules and on to quantum dots. We examine the transition to facile vibrational energy flow in a large set of organic molecules as molecular size is increased. Both analytical and computational results based on local random matrix models describe the transition to unrestricted vibrational energy flow in these molecules. In particular, the models connect the number of states participating in intramolecular energy flow to simple molecular properties such as the molecular size and the distribution of vibrational frequencies. The transition itself is governed by a local anharmonic coupling strength and a local state density. The theoretical results for the transition characteristics compare well with those implied by experimental measurements using IR fluorescence spectroscopy of dilution factors reported by Stewart and McDonald [Stewart, G. M. and McDonald, J. D. (1983) J. Chem. Phys. 78, 3907-3915].

Original languageEnglish (US)
Pages (from-to)5960-5964
Number of pages5
JournalProceedings of the National Academy of Sciences of the United States of America
Issue number11
StatePublished - May 26 1998

ASJC Scopus subject areas

  • General

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