Solving the unimolecular master equation with a weighted subspace projection method

Frankcombe, T. J. and Smith, S. C. (2000) Solving the unimolecular master equation with a weighted subspace projection method. Journal of Computational Chemistry, 21 8: 592-606. doi:10.1002/(SICI)1096-987X(200006)21:8<592::AID-JCC2>3.3.CO;2-U


Author Frankcombe, T. J.
Smith, S. C.
Title Solving the unimolecular master equation with a weighted subspace projection method
Journal name Journal of Computational Chemistry   Check publisher's open access policy
ISSN 0192-8651
Publication date 2000-01-01
Sub-type Article (original research)
DOI 10.1002/(SICI)1096-987X(200006)21:8<592::AID-JCC2>3.3.CO;2-U
Volume 21
Issue 8
Start page 592
End page 606
Total pages 15
Place of publication New York
Publisher Wiley
Language eng
Subject C1
250600 Theoretical and Computational Chemistry
780103 Chemical sciences
Abstract A weighted subspace projection method for solving the unimolecular master equation over a wide range of temperatures and pressures is developed. Sample calculations modeling the dissociation of ethane at 300 K and pressures as low as 0.65 Torr demonstrates the utility of the method in regimes where standard projection methods fail. For the sample calculations the weighted Arnoldi method was able to reliably calculate the smallest eigenvalue of the rate matrix in excellent agreement with calculations using the Nesbet algorithm. Extremely small eigenvalues of the order of -10(-48) could be calculated without difficulty. The formal equivalence between various weighting schemes and common matrix transformations is shown. The point that merely taking the transpose of the rate matrix can be extremely beneficial is made, commenting on the relationship between the left and right eigenvectors of the rate matrix. (C) 2000 John Wiley & Sons, Inc.
Keyword Chemistry, Multidisciplinary
Master Equations
Arnoldi Method
Eigenproblem
Weighting
Wipsp Method
Energy-transfer
Q-Index Code C1

Document type: Journal Article
Sub-type: Article (original research)
Collection: School of Chemistry and Molecular Biosciences
 
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Created: Tue, 10 Jun 2008, 22:07:18 EST