### Abstract

A theory for the statistical equilibration of the degenerate vibrational modes of a polyatomic molecule is presented. It is shown how combined radiative and bimolecular collisional development of the degenerate multimode system may be related to that of the single-mode system. Exact multimode rate equations are derived and used to demonstrate that for the ideal harmonic system only transient disturbances of quasithermal equilibrium are permitted. A model theory for the truncated harmonic system in terms of rate equations for the first and second population distribution moments is studied. A solution is presented and related to recent experimental studies of cyclobutanone.

Original language | English |
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Article number | 015 |

Pages (from-to) | 3787-3796 |

Number of pages | 10 |

Journal | Journal of Physics B: Atomic and Molecular Physics |

Volume | 16 |

Issue number | 20 |

DOIs | |

Publication status | Published - 1983 |

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### Cite this

*Journal of Physics B: Atomic and Molecular Physics*,

*16*(20), 3787-3796. [015]. https://doi.org/10.1088/0022-3700/16/20/015

}

*Journal of Physics B: Atomic and Molecular Physics*, vol. 16, no. 20, 015, pp. 3787-3796. https://doi.org/10.1088/0022-3700/16/20/015

**Theory of collisional equilibration of a radiatively excited molecular gas.** / Harper, P. G.

Research output: Contribution to journal › Article

TY - JOUR

T1 - Theory of collisional equilibration of a radiatively excited molecular gas

AU - Harper, P. G.

PY - 1983

Y1 - 1983

N2 - A theory for the statistical equilibration of the degenerate vibrational modes of a polyatomic molecule is presented. It is shown how combined radiative and bimolecular collisional development of the degenerate multimode system may be related to that of the single-mode system. Exact multimode rate equations are derived and used to demonstrate that for the ideal harmonic system only transient disturbances of quasithermal equilibrium are permitted. A model theory for the truncated harmonic system in terms of rate equations for the first and second population distribution moments is studied. A solution is presented and related to recent experimental studies of cyclobutanone.

AB - A theory for the statistical equilibration of the degenerate vibrational modes of a polyatomic molecule is presented. It is shown how combined radiative and bimolecular collisional development of the degenerate multimode system may be related to that of the single-mode system. Exact multimode rate equations are derived and used to demonstrate that for the ideal harmonic system only transient disturbances of quasithermal equilibrium are permitted. A model theory for the truncated harmonic system in terms of rate equations for the first and second population distribution moments is studied. A solution is presented and related to recent experimental studies of cyclobutanone.

UR - http://www.scopus.com/inward/record.url?scp=36149041436&partnerID=8YFLogxK

U2 - 10.1088/0022-3700/16/20/015

DO - 10.1088/0022-3700/16/20/015

M3 - Article

VL - 16

SP - 3787

EP - 3796

JO - Journal of Physics B: Atomic and Molecular Physics

JF - Journal of Physics B: Atomic and Molecular Physics

SN - 0022-3700

IS - 20

M1 - 015

ER -