Dynamics of ethyl radical decomposition. 3. Effect of chemical activation vs. microcanonical sampling

William L. Hase; Daniel G. Buckowski; Kandadai N. Swamy

doi:10.1021/j100238a014

Dynamics of ethyl radical decomposition. 3. Effect of chemical activation vs. microcanonical sampling

William L. Hase, Daniel G. Buckowski, Kandadai N. Swamy

Chemistry and Biochemistry

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Abstract

Formation and decomposition of chemically activated ethyl radicals is simulated by the Monte Carlo quasiclassical trajectory method. The results are compared with a previous study of a microcanonical ensemble of ethyl radicals. Chemically activated ethyl radicals have an apparent non-RRKM lifetime distribution as a result of nonrandom excitation. However, rapid intramolecular relaxation processes give a lifetime distribution after approximately 5 × 10^-12 s which agrees with that for a microcanonical ensemble. A statistical model for partitioning of energy and angular momenta at the dissociation barrier is given, and the trajectory results agree with the predictions of the model.

Original language	English
Pages (from-to)	2754-2763
Number of pages	10
Journal	Journal of physical chemistry
Volume	87
Issue number	15
DOIs	https://doi.org/10.1021/j100238a014
State	Published - 1983

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title = "Dynamics of ethyl radical decomposition. 3. Effect of chemical activation vs. microcanonical sampling",

abstract = "Formation and decomposition of chemically activated ethyl radicals is simulated by the Monte Carlo quasiclassical trajectory method. The results are compared with a previous study of a microcanonical ensemble of ethyl radicals. Chemically activated ethyl radicals have an apparent non-RRKM lifetime distribution as a result of nonrandom excitation. However, rapid intramolecular relaxation processes give a lifetime distribution after approximately 5 × 10-12 s which agrees with that for a microcanonical ensemble. A statistical model for partitioning of energy and angular momenta at the dissociation barrier is given, and the trajectory results agree with the predictions of the model.",

author = "Hase, {William L.} and Buckowski, {Daniel G.} and Swamy, {Kandadai N.}",

year = "1983",

doi = "10.1021/j100238a014",

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volume = "87",

pages = "2754--2763",

journal = "Journal of physical chemistry",

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T1 - Dynamics of ethyl radical decomposition. 3. Effect of chemical activation vs. microcanonical sampling

AU - Hase, William L.

AU - Buckowski, Daniel G.

AU - Swamy, Kandadai N.

PY - 1983

Y1 - 1983

N2 - Formation and decomposition of chemically activated ethyl radicals is simulated by the Monte Carlo quasiclassical trajectory method. The results are compared with a previous study of a microcanonical ensemble of ethyl radicals. Chemically activated ethyl radicals have an apparent non-RRKM lifetime distribution as a result of nonrandom excitation. However, rapid intramolecular relaxation processes give a lifetime distribution after approximately 5 × 10-12 s which agrees with that for a microcanonical ensemble. A statistical model for partitioning of energy and angular momenta at the dissociation barrier is given, and the trajectory results agree with the predictions of the model.

AB - Formation and decomposition of chemically activated ethyl radicals is simulated by the Monte Carlo quasiclassical trajectory method. The results are compared with a previous study of a microcanonical ensemble of ethyl radicals. Chemically activated ethyl radicals have an apparent non-RRKM lifetime distribution as a result of nonrandom excitation. However, rapid intramolecular relaxation processes give a lifetime distribution after approximately 5 × 10-12 s which agrees with that for a microcanonical ensemble. A statistical model for partitioning of energy and angular momenta at the dissociation barrier is given, and the trajectory results agree with the predictions of the model.

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U2 - 10.1021/j100238a014

DO - 10.1021/j100238a014

M3 - Article

AN - SCOPUS:0001656246

SN - 0022-3654

VL - 87

SP - 2754

EP - 2763

JO - Journal of physical chemistry

JF - Journal of physical chemistry

IS - 15

ER -

Dynamics of ethyl radical decomposition. 3. Effect of chemical activation vs. microcanonical sampling

Abstract

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