TITLE

The definition of reaction coordinates for reaction-path dynamics

AUTHOR(S)
Natanson, Gregory A.; Garrett, Bruce C.; Truong, Thanh N.; Joseph, Tomi; Truhlar, Donald G.
PUB. DATE
June 1991
SOURCE
Journal of Chemical Physics;6/15/1991, Vol. 94 Issue 12, p7875
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
We present equations for generalized-normal-mode vibrational frequencies in reaction-path calculations based on various sets of coordinates for describing the internal motions of the system in the vicinity of a reaction path. We consider two special cases in detail as examples, in particular three-dimensional atom–diatom collisions with collinear steepest descent paths and reactions of the form CX3+YZ→CX3 Y+Z with reaction paths having C3v symmetry. We then present numerical comparisons of the differences in harmonic reaction-path frequencies for various coordinate choices for three such systems, namely, H+H2→H2+H, O+H2→OH+H, and CH3+H2→CH4+H. We test the importance of the differences in the harmonic frequencies for dynamics calculations by using them to compute thermal rate constants using variational transition state theory with semiclassical ground-state tunneling corrections. We present a new coordinate system for the reaction CH3+H2 that should allow for more accurate calculations than the Cartesian system used for previous reaction-path calculations on this and other polyatomic systems.
ACCESSION #
7640957

 

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