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A comparison of two‐dimensional and three‐dimensional trajectory calculations in thermal HBr 2 and H 2 Br systems
Author(s) -
Pace S. A.,
White J. M.
Publication year - 1975
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550070614
Subject(s) - trajectory , chemistry , curse of dimensionality , phase space , invariant (physics) , scattering , thermal , atomic physics , thermodynamics , physics , quantum mechanics , statistics , mathematics
Two‐dimensional (2D) and three‐dimensional (3D) quasiclassical trajectory calculations on H + Br 2 at 300°K and H + HBr at 1000°K are reported. Angular scattering, energy disposal, and impact parameter distributions for reactive collisions are compared after removal of phase‐space factors (dimensionality bias) as a means of examining the similarities and differences in the dynamic bias in 2D and 3D. Qualitatively, for all reactive processes studied, the 3D trajectory calculated distributions are reproduced by the phase‐space adjusted 2D trajectory data. Thus the surprisal of these angular scattering, energy disposal, and impact parameter distributions is dimensionally invariant, and the same dynamic bias appears in 2D and 3D. A systematic method for converting 2D reaction probabilities and maximum reactive impact parameters into 3D rate coefficients is presented. We find that trajectory calculated 3D rate coefficients may in general differ markedly from those derived from 2D trajectory data. In particular, the surprisal associated with rate coefficients depends on dimensionality for the H + HBr → H 2 + Br reaction, but is invariant for the H′ + HBr → H′Br + Br and H + Br 2 → HBr + Br reactions.