Document Detail


State-to-state reaction probabilities within the quantum transition state framework.
MedLine Citation:
PMID:  22360179     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
Rigorous quantum dynamics calculations of reaction rates and initial state-selected reaction probabilities of polyatomic reactions can be efficiently performed within the quantum transition state concept employing flux correlation functions and wave packet propagation utilizing the multi-configurational time-dependent Hartree approach. Here, analytical formulas and a numerical scheme extending this approach to the calculation of state-to-state reaction probabilities are presented. The formulas derived facilitate the use of three different dividing surfaces: two dividing surfaces located in the product and reactant asymptotic region facilitate full state resolution while a third dividing surface placed in the transition state region can be used to define an additional flux operator. The eigenstates of the corresponding thermal flux operator then correspond to vibrational states of the activated complex. Transforming these states to reactant and product coordinates and propagating them into the respective asymptotic region, the full scattering matrix can be obtained. To illustrate the new approach, test calculations study the D + H(2)(ν, j) → HD(ν', j') + H reaction for J = 0.
Authors:
Ralph Welsch; Fermín Huarte-Larrañaga; Uwe Manthe
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Publication Detail:
Type:  JOURNAL ARTICLE    
Journal Detail:
Title:  The Journal of chemical physics     Volume:  136     ISSN:  1089-7690     ISO Abbreviation:  -     Publication Date:  2012 Feb 
Date Detail:
Created Date:  2012-2-24     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  0375360     Medline TA:  J Chem Phys     Country:  -    
Other Details:
Languages:  ENG     Pagination:  064117     Citation Subset:  -    
Affiliation:
Theoretische Chemie, Fakultät für Chemie, Universität Bielefeld, Universitätsstr. 25, D-33615 Bielefeld, Germany.
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