Abstract
Earlier work of the authors [J. Chem. Phys. 77, 2378 (1982)] has shown how the reaction path Hamiltonian of Miller, Handy, and Adams [J. Chem. Phys. 72, 99 (1980)] can be divided into a "system" of the reaction coordinate and modes strongly coupled to it, plus a "bath" of more weakly coupled modes. Quantum mechanical perturbation theory was used to show how one can combine an exact description of the system dynamics with an approximate (perturbative) treatment of the effect of the bath. The present paper applies this approach to the 3d H+H2 reaction, where the two collinear degrees of freedom constitute the system, and the two bending modes the bath. Comparison with the accurate scattering calculations of Schatz and Kupermann [J. Chem. Phys. 65, 4668 (1976)] shows it to provide a good description of the coupling between bending (i.e., rotational) and collinear modes.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 3759-3764 |
| Number of pages | 6 |
| Journal | The Journal of Chemical Physics |
| Volume | 79 |
| Issue number | 8 |
| State | Published - 1983 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Atomic and Molecular Physics, and Optics
Cite this
System-bath decomposition of the reaction path Hamiltonian. II. Rotationally inelastic reactive scattering of H+H2 in three dimensions. / Schwartz, Steven D; Miller, William H.
In: The Journal of Chemical Physics, Vol. 79, No. 8, 1983, p. 3759-3764.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - System-bath decomposition of the reaction path Hamiltonian. II. Rotationally inelastic reactive scattering of H+H2 in three dimensions
AU - Schwartz, Steven D
AU - Miller, William H.
PY - 1983
Y1 - 1983
N2 - Earlier work of the authors [J. Chem. Phys. 77, 2378 (1982)] has shown how the reaction path Hamiltonian of Miller, Handy, and Adams [J. Chem. Phys. 72, 99 (1980)] can be divided into a "system" of the reaction coordinate and modes strongly coupled to it, plus a "bath" of more weakly coupled modes. Quantum mechanical perturbation theory was used to show how one can combine an exact description of the system dynamics with an approximate (perturbative) treatment of the effect of the bath. The present paper applies this approach to the 3d H+H2 reaction, where the two collinear degrees of freedom constitute the system, and the two bending modes the bath. Comparison with the accurate scattering calculations of Schatz and Kupermann [J. Chem. Phys. 65, 4668 (1976)] shows it to provide a good description of the coupling between bending (i.e., rotational) and collinear modes.
AB - Earlier work of the authors [J. Chem. Phys. 77, 2378 (1982)] has shown how the reaction path Hamiltonian of Miller, Handy, and Adams [J. Chem. Phys. 72, 99 (1980)] can be divided into a "system" of the reaction coordinate and modes strongly coupled to it, plus a "bath" of more weakly coupled modes. Quantum mechanical perturbation theory was used to show how one can combine an exact description of the system dynamics with an approximate (perturbative) treatment of the effect of the bath. The present paper applies this approach to the 3d H+H2 reaction, where the two collinear degrees of freedom constitute the system, and the two bending modes the bath. Comparison with the accurate scattering calculations of Schatz and Kupermann [J. Chem. Phys. 65, 4668 (1976)] shows it to provide a good description of the coupling between bending (i.e., rotational) and collinear modes.
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M3 - Article
VL - 79
SP - 3759
EP - 3764
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 8
ER -