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 language | English |
|---|---|
| Pages (from-to) | 1141-1159 |
| Number of pages | 19 |
| Journal | Journal of Chemical Physics |
| Volume | 66 |
| Issue number | 3 |
| Publication status | Published - 1977 |
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ASJC Scopus subject areas
- Atomic and Molecular Physics, and Optics
Cite this
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 journal › Article
}
TY - JOUR
T1 - A systematic treatment of quantum mechanical reaction coordinates
AU - Witriol, N. M.
AU - Stettler, J. D.
AU - Ratner, Mark A
AU - Sabin, J. R.
AU - Trickey, S. B.
PY - 1977
Y1 - 1977
N2 - 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.
AB - 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.
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M3 - Article
VL - 66
SP - 1141
EP - 1159
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 3
ER -