Quantum mechanical calculation of resonance tunneling in acetylene isomerization via the vinylidene intermediate
- Department of Chemistry, University of California, Berkeley, California 94720-1460 (United States)
Microcanonical rate constants for the acetylene isomerization reaction have been computed using the direct cumulative reaction probability methodology of Seideman and Miller [J. Chem. Phys. {bold 96}, 4412 (1992); {bold 97}, 2499 (1992)] and Manthe and Miller [J. Chem. Phys. {bold 99}, 3411 (1993)]. Two- and three-degree-of-freedom calculations are reported using a normal mode Hamiltonian based on the geometry of the vinylidene intermediate. Due to the vinylidene well, numerous resonances are found in the isomerization rate. Little coupling is found between the CH{sub 2} rock reaction coordinate and the other normal modes, so that the resonances are readily assignable as normal mode progressions. Qualitatively similar results are obtained using two different potential energy surfaces, or different reduced dimensionality sets of coordinates. {copyright} {ital 1998 American Institute of Physics.} thinsp
- OSTI ID:
- 636139
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 1 Vol. 109; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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