Document Detail


Semiclassical instanton approach to calculation of reaction rate constants in multidimensional chemical systems.
MedLine Citation:
PMID:  21428603     Owner:  NLM     Status:  In-Data-Review    
Abstract/OtherAbstract:
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.
Authors:
Maksym Kryvohuz
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Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  The Journal of chemical physics     Volume:  134     ISSN:  1089-7690     ISO Abbreviation:  J Chem Phys     Publication Date:  2011 Mar 
Date Detail:
Created Date:  2011-03-24     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  0375360     Medline TA:  J Chem Phys     Country:  United States    
Other Details:
Languages:  eng     Pagination:  114103     Citation Subset:  IM    
Affiliation:
Arthur Amos Noyes Laboratory of Chemical Physics, 127-72, California Institute of Technology, Pasadena, California 91125, USA.
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