A systematic treatment of quantum mechanical reaction coordinates

N. M. Witriol, J. D. Stettler, Mark A Ratner, J. R. Sabin, S. B. Trickey

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

The problem of constructing an orthogonal curvilinear coordinate system which retains the intuitive clarity of the reaction path concept is treated by canonical point transformation. The Hamiltonian describing the collision process is transformed rigorously onto the reaction-coordinate net; no linearization or approximation is employed. Difficulties inherent in earlier work (e.g., triple-valued regions, restriction to regions very close to the reaction path, etc.) do not occur. The transformed momenta and Hamiltonian are obtained in general. A simple, yet useful, example transformation is worked out in detail and applied to a realistic problem, the LEPS potential surface for H+Cl 2→HCl+Cl. The example transformation is also used in a comparison of our method with that of Marcus. The canonical mapping of Connor and Marcus is shown to be a special case of the present method. Applications of the procedure to polydimensional surfaces, dissociative reactions, and actual dynamical calculations are discussed.

Original languageEnglish
Pages (from-to)1141-1159
Number of pages19
JournalJournal of Chemical Physics
Volume66
Issue number3
Publication statusPublished - 1977

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Hamiltonians
Surface reactions
Linearization
Momentum
clarity
spherical coordinates
linearization
surface reactions
constrictions
momentum
collisions
approximation

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Witriol, N. M., Stettler, J. D., Ratner, M. A., Sabin, J. R., & Trickey, S. B. (1977). A systematic treatment of quantum mechanical reaction coordinates. Journal of Chemical Physics, 66(3), 1141-1159.

A systematic treatment of quantum mechanical reaction coordinates. / Witriol, N. M.; Stettler, J. D.; Ratner, Mark A; Sabin, J. R.; Trickey, S. B.

In: Journal of Chemical Physics, Vol. 66, No. 3, 1977, p. 1141-1159.

Research output: Contribution to journalArticle

Witriol, NM, Stettler, JD, Ratner, MA, Sabin, JR & Trickey, SB 1977, 'A systematic treatment of quantum mechanical reaction coordinates', Journal of Chemical Physics, vol. 66, no. 3, pp. 1141-1159.
Witriol NM, Stettler JD, Ratner MA, Sabin JR, Trickey SB. A systematic treatment of quantum mechanical reaction coordinates. Journal of Chemical Physics. 1977;66(3):1141-1159.
Witriol, N. M. ; Stettler, J. D. ; Ratner, Mark A ; Sabin, J. R. ; Trickey, S. B. / A systematic treatment of quantum mechanical reaction coordinates. In: Journal of Chemical Physics. 1977 ; Vol. 66, No. 3. pp. 1141-1159.
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