### Abstract

A chemical dynamics simulation was performed to model experiments [N. A. West et al., J. Chem. Phys. 145, 014308 (2016)] in which benzene molecules are vibrationally excited to 148.1 kcal/mol within a N_{2}-benzene bath. A significant fraction of the benzene molecules are excited, resulting in heating of the bath, which is accurately represented by the simulation. The interesting finding from the simulations is the non-statistical collisional energy transfer from the vibrationally excited benzene C_{6}H_{6} ^{∗} molecules to the bath. The simulations find that at ∼10^{-7} s and 1 atm pressure there are four different final temperatures for C_{6}H_{6} ^{∗} and the bath. N_{2} vibration is not excited and remains at the original bath temperature of 300 K. Rotation and translation degrees of freedom of both N_{2} and C_{6}H_{6} in the bath are excited to a final temperature of ∼340 K. Energy transfer from the excited C_{6}H_{6} ^{∗} molecules is more efficient to vibration of the C_{6}H_{6} bath than its rotation and translation degrees of freedom, and the final vibrational temperature of the C_{6}H_{6} bath is ∼453 K, if the average energy of each C_{6}H_{6} vibration mode is assumed to be RT. There is no vibrational equilibration between C_{6}H_{6} ^{∗} and the C_{6}H_{6} bath molecules. When the simulations are terminated, the vibrational temperatures of the C_{6}H_{6} ^{∗} and C_{6}H_{6} bath molecules are ∼537 K and ∼453 K, respectively. An important question is the time scale for complete energy equilibration of the C_{6}H_{6} ^{∗} and N_{2} and C_{6}H_{6} bath system. At 1 atm and 300 K, the experimental V-T (vibration-translation) relaxation time for N_{2} is ∼10^{-4} s. The simulation time was too short for equilibrium to be attained, and the time for complete equilibration of C_{6}H_{6} ^{∗} vibration with translation, rotation, and vibration of the bath was not determined.

Original language | English |
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Article number | 134101 |

Journal | Journal of Chemical Physics |

Volume | 149 |

Issue number | 13 |

DOIs | |

State | Published - Oct 7 2018 |

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## Cite this

*Journal of Chemical Physics*,

*149*(13), [134101]. https://doi.org/10.1063/1.5043139