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Computational methods for reactive scattering
Author(s) -
Redmon Michael J.,
Wyatt Robert E.
Publication year - 2009
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560120841
Subject(s) - scattering , adiabatic process , unitarity , resonance (particle physics) , unimodular matrix , matrix (chemical analysis) , s matrix , basis (linear algebra) , physics , quantum , chemistry , atomic physics , quantum mechanics , mathematics , geometry , discrete mathematics , chromatography
Two methods of obtaining unimodular sector transformation matrices required in quantum scattering calculations employing locally adiabatic basis sets are discussed, one being particularly useful for three‐dimensional reactive scattering. These are shown to lead to improved unitarity and detailed balance in a computed S ‐matrix. New results arc presented for the H + D 2 , and F + H 2 reactions, including total cross sections obtained within a J 2 ‐conserving approximation. In particular, evidence is presented which indicates that the strong n = 2 vibrational resonance appearing in collinear studies of the F + H 2 reaction is drastically affected by rotational broadening, indicating that collinear studies of exoergic reactions may be of limited practical utility in predicting resonance widths.