Abstract
A time-independent quantum scattering method has been used to study intersystem crossing (ISC) effects in the bimolecular reaction O + H2. Our studies, involving a four-state one dimensional model, give fully coupled reaction probabilities that indicate significant quantum effects, including enhanced tunneling for the ground state reaction, significant Stuckelberg oscillations at energies well above threshold for certain states, and strong mixing of the product spin-orbit populations that leads to statistical behavior for some initial states and even inverted populations in some cases. Comparison of these results with those from a recently developed trajectory surface hopping (TSH) method which uses a “mixed” representation in full dimensionality are examined, and we conclude that the one-dimensional model overemphasizes coherence and interference effects, although many of the same effects occur.
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References
Alagia, M., Balucani, N., Cartechini, L., Casavecchia, P., van Beek, M., Volpi, G.C., Bennet, L. and Rayez, J. C. (1999) Crossed beam studies of the O(3P,1D) + CH3I reactions: Direct evidence of intersystem crossing, Faraday Discuss 113, pp. 133–150.
Zhang, X.-G., Rue, C., Shin, S.-Y. and Armentrout, P.B. (2002) Reaction of Ta+ and W+ with H2, D2, and HD: Effect of lanthanide contraction and spin-orbit interactions on reactivity and thermochemistry, J. Chem. Phys. 116, pp. 5574–5583.
Hoffmann, M.R. and Schatz, G.C. (2000) Theoretical studies of intersystem crossing effects in the O + H2 reaction, J. Chem. Phys. 113, pp. 9456–9465.
Donaldson, D.J. and Wright, J.S. (1984) Singlet-triplet surface crossings and low-temperature rate enhancement for O(3)P) + H2 → OH + H, J. Chem. Phys. 80, pp. 221–231.
Maiti, B. and Schatz, G.C. (2003) Theoretical studies of intersystem crossing effects in the nonadiabatic dynamics of bimolecular reactions, J. Chem. Phys. — to be submitted.
Rogers, S., Wang, D., Kuppermann, A. and Walch, S. (2000) Chemically Accurate ab Initio Potential Energy Surfaces for the Lowest 3A′ and 3A″ Electronically Adiabatic States of O(3p) + H2, J. Phys. Chem. A 104, 2308–2325.
Schatz, G.C. (1995) Influence of atomic fine structure on bimolecular rate constants: The CI(2P) + HCI reaction, J. Phys. Chem. 99, pp. 7522–7529.
Hoffmann, M.R. and Schatz, G.C. (2002) Model Studies of Intersystem Crossing Effects in the O + H2 Reaction, in Low-Lying Potential Energy Surfaces, M.R. Hoffmann and K.G. Dyall eds., ACS Symposium Series 828, pp. 329–345.
Garton, D. J., Minton, T. K., Maiti, B., Troya, D., Schatz, G.C. (2003) A crossed molecular beams study of the O(3P) + H2 reaction: comparison of excitation function with accurate quantum reactive scattering calculations, J. Chem. Phys. 118, pp. 1585–1588.
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Maiti, B., Schatz*, G.C. (2004). Non-Adiabatic Dynamics in the O+H2 Reaction: A Timeindependent Quantum Mechanical Study. In: Lagana, A., Lendvay, G. (eds) Theory of Chemical Reaction Dynamics. NATO Science Series II: Mathematics, Physics and Chemistry, vol 145. Springer, Dordrecht. https://doi.org/10.1007/1-4020-2165-8_4
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DOI: https://doi.org/10.1007/1-4020-2165-8_4
Publisher Name: Springer, Dordrecht
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