DOI: 10.1073/pnas.95.11.5960. The vibrational energy flow transition in organic molecules: Theory meets experiment

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

10.1073/pnas.95.11.5960

Crossref journal-article

Proceedings of the National Academy of Sciences

Proceedings of the National Academy of Sciences (341)

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 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. & McDonald, J. D. (1983) J. Chem. Phys. 78, 3907–3915].

Bibliography

Bigwood, R., Gruebele, M., Leitner, D. M., & Wolynes, P. G. (1998). The vibrational energy flow transition in organic molecules: Theory meets experiment. Proceedings of the National Academy of Sciences, 95(11), 5960â5964.

Authors 4

R. Bigwood (first)
M. Gruebele (additional)
D. M. Leitner (additional)
P. G. Wolynes (additional)

References 24 Referenced 97

10.1016/0370-1573(91)90140-H
10.1063/1.1700424
10.1063/1.447006
10.1063/1.467230
10.1063/1.470149
10.1063/1.471531
10.1146/annurev.pc.45.100194.001325
10.1063/1.464843
10.1103/PhysRevA.54.2066
10.1103/PhysRevLett.78.2803
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10.1103/PhysRevLett.76.216
10.1063/1.473253
Gruebele M. & Bigwood R. (1998) Int. Rev. Phys. Chem. in press.
10.1021/jp960443i
R Bigwood, M Gruebele ACH Models in Chemistry 134, 637–661 (1997). / ACH Models in Chemistry by Bigwood R (1997)
Pearman R. & Gruebele M. (1998) J. Chem. Phys. in press.
10.1063/1.1701809
10.1016/S0009-2614(97)01120-2

Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 10:40 a.m.)
Deposited	3 years, 4 months ago (April 13, 2022, 3:50 p.m.)
Indexed	31 minutes ago (Sept. 2, 2025, 4:43 p.m.)
Issued	27 years, 3 months ago (May 26, 1998)
Published	27 years, 3 months ago (May 26, 1998)
Published Online	27 years, 3 months ago (May 26, 1998)
Published Print	27 years, 3 months ago (May 26, 1998)

Funders 0

None

BibTeX

@article{Bigwood_1998, title={The vibrational energy flow transition in organic molecules: Theory meets experiment}, volume={95}, ISSN={1091-6490}, url={http://dx.doi.org/10.1073/pnas.95.11.5960}, DOI={10.1073/pnas.95.11.5960}, number={11}, journal={Proceedings of the National Academy of Sciences}, publisher={Proceedings of the National Academy of Sciences}, author={Bigwood, R. and Gruebele, M. and Leitner, D. M. and Wolynes, P. G.}, year={1998}, month=may, pages={5960–5964} }

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