Semiclassical instanton approach to calculation of reaction rate constants in multidimensional chemical systems
- Creators
- Kryvohuz, Maksym
Abstract
The semiclassical instanton approximation is revisited in the context of its application to the calculation of chemical reaction rate constants. An analytical expression for the quantum canonical reaction rate constants of multidimensional systems is derived for all temperatures from the deep tunneling to high-temperature regimes. The connection of the derived semiclassical instanton theory with several previously developed reaction rate theories is shown and the numerical procedure for the search of instanton trajectories is provided. The theory is tested on seven different collinear symmetric and asymmetric atom transfer reactions including heavy-light-heavy, light-heavy-light and light-light-heavy systems. The obtained thermal rate constants agree within a factor of 1.5–2 with the exact quantum results in the wide range of temperatures from 200 to 1500 K.
Additional Information
© 2011 American Institute of Physics. Received 29 October 2010; accepted 23 February 2011; published online 17 March 2011. I would like to acknowledge the vital contribution of Professor Rudy Marcus to this paper. His stimulating discussions and encouragement at all stages of the project have insured its progress. I am also pleased to acknowledge the support of the James W. Glanville Fellowship fund, and of the several granting agencies supporting research of the R. A. Marcus group, ONR, NSF, and ARO.Attached Files
Published - Kryvohuz2011p13365J_Chem_Phys.pdf
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Additional details
- Eprint ID
- 23338
- Resolver ID
- CaltechAUTHORS:20110414-105348670
- James W. Glanville Fellowship Fund
- Office of Naval Research (ONR)
- NSF
- Army Research Office (ARO)
- Created
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2011-04-14Created from EPrint's datestamp field
- Updated
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2021-11-09Created from EPrint's last_modified field