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Titolo:
THE VIBRATIONAL-ENERGY FLOW TRANSITION IN ORGANIC-MOLECULES - THEORY MEETS EXPERIMENT
Autore:
BIGWOOD R; GRUEBELE M; LEITNER DM; WOLYNES PG;
Indirizzi:
UNIV ILLINOIS,DEPT CHEM,1209 W CALIF ST URBANA IL 61801 UNIV ILLINOIS,DEPT CHEM URBANA IL 61801 UNIV ILLINOIS,BECKMAN INST ADV SCI & TECHNOL URBANA IL 61801
Titolo Testata:
Proceedings of the National Academy of Sciences of the United Statesof America
fascicolo: 11, volume: 95, anno: 1998,
pagine: 5960 - 5964
SICI:
0027-8424(1998)95:11<5960:TVFTIO>2.0.ZU;2-U
Fonte:
ISI
Lingua:
ENG
Soggetto:
REDISTRIBUTION; RELAXATION; DYNAMICS; SPECTRA; SYSTEMS; MODEL;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Science Citation Index Expanded
Citazioni:
24
Recensione:
Indirizzi per estratti:
Citazione:
R. Bigwood et al., "THE VIBRATIONAL-ENERGY FLOW TRANSITION IN ORGANIC-MOLECULES - THEORY MEETS EXPERIMENT", Proceedings of the National Academy of Sciences of the United Statesof America, 95(11), 1998, pp. 5960-5964

Abstract

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 ina large set of organic molecules as molecular size is increased. Bothanalytical and computational results based on local random matrix models describe the transition to unrestricted vibrational energy flow inthese 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 vibrationalfrequencies. 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.

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Documento generato il 28/09/20 alle ore 16:10:44