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Specific Rate Constants of Unimolecular Processes II. Adiabatic Channel Model
Abstract
The rate of unimolecular processes is calculated by means of a statistical adiabatic channel model. The rates are mainly determined by the maxima of the channel energies. The channels are constructed by correlating reactant and product states; the channel energies are computed by a simple interpolation procedure. The coupling between the various vibrational‐rotational motions is taken into account. The influence of parameters of the potential surface on channel energies and on rate constants is studied. Numerical results for the NO 2, CH 4, CD 4, C 2 H 6 and C 2 D 6 dissociation – recombination kinetics are compared to experimental data. The statistical adiabatic channel model gives similar results as minimum local entropy models. Both these approaches lead to stronger curvatures of k(E) and smaller activation energies for the thermal rate constant k∞ than the corresponding RRKM calculations.
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Cited by
Current Status of Transition-State Theory
Truhlar, D. G., Garrett, B. C., & Klippenstein, S. J. (1996) · The Journal of Physical Chemistry · doi:10.1021/jp953748q · Cited by 2,279
Quack, M., & Suhm, M. A. (1991) · The Journal of Chemical Physics · doi:10.1063/1.461486 · Cited by 295
Self-citationDuncan, W. T., Bell, R. L., & Truong, T. N. (1998) · Journal of Computational Chemistry · doi:10.1002/(sici)1096-987x(19980715)19:9<1039::aid-jcc5>3.0.co;2-r · Cited by 285
State-resolved probes of methane dissociation dynamics
Juurlink, L. B. F., Killelea, D. R., & Utz, A. L. (2009) · Progress in Surface Science · doi:10.1016/j.progsurf.2009.01.001 · Cited by 255
Metadata
- Authors
- Quack, M., & Troe, J.
- Venue
- Berichte der Bunsengesellschaft für physikalische Chemie
- Publisher
- Wiley
- Published
- 1974-03
- Volume
- 78
- Issue
- 3
- Pages
- 240-252
- ISSN
- 0005-9021 (ISSN-L)
- OpenAlex
- W2149955703
- Cited by
- 588
- References
- 0
- FWCI
- 13.09
- Type
- journal article
- Language
- en
- Open access
- closed
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- Quack, M., & Troe, J. (1974). Specific Rate Constants of Unimolecular Processes II. Adiabatic Channel Model. Berichte der Bunsengesellschaft für physikalische Chemie. https://doi.org/10.1002/bbpc.19740780306
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