Published October 26, 2006
| Version v1
Journal article
Quantum theory of enhanced unimolecular reaction rates below the ergodicity threshold
Creators
- 1. Department of Chemistry and Chemical Physics Program, University of Nevada, Reno, Mail Stop 216, 1664 N. Virginia St., Reno, NV 89557 (United States)
- 2. Department of Chemistry and Biochemistry and Department of Physics, University of California, San Diego, La Jolla, CA 92093 (United States)
Description
A variety of unimolecular reactions exhibit measured rates that exceed Rice-Ramsperger-Kassel-Marcus (RRKM) predictions. We show using the local random matrix theory (LRMT) of vibrational energy flow how the quantum localization of the vibrational states of a molecule, by violating the ergodicity assumption, can give rise to such an enhancement of the apparent reaction rate. We present an illustrative calculation using LRMT for a model 12-vibrational mode organic molecule to show that below the ergodicity threshold the reaction rate may exceed many times the RRKM prediction due to quantum localization of vibrational states
Additional details
Identifiers
- DOI
- 10.1016/j.chemphys.2006.05.013;
- PII
- S0301-0104(06)00289-8;
Publishing Information
- Journal Title
- Chemical Physics
- Journal Volume
- 329
- Journal Issue
- 1-3
- Journal Page Range
- p. 163-167
- ISSN
- 0301-0104
- CODEN
- CMPHC2
INIS
- Country of Publication
- Netherlands
- Country of Input or Organization
- International Atomic Energy Agency (IAEA)
- INIS RN
- 39096831
- Subject category
- S74: ATOMIC AND MOLECULAR PHYSICS;
- Descriptors DEI
- FORECASTING; MATRICES; MOLECULES; QUANTUM MECHANICS; RANDOMNESS; REACTION KINETICS; VIBRATIONAL STATES
- Descriptors DEC
- ENERGY LEVELS; EXCITED STATES; KINETICS; MECHANICS
Optional Information
- Copyright
- Copyright (c) 2006 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.