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Trajectory simulations of collisional energy transfer in highly excited benzene and hexafluorobenzene
journal contribution
posted on 1995-07-08, 00:00 authored by T Lenzer, K Luther, J Troe, R G Gilbert, Kieran LimKieran LimQuasiclassical trajectory calculations of the energy transfer of highly vibrationally excited benzene and hexafluorobenzene (HFB) molecules colliding with helium, argon and xenon have been performed. Deactivation is found to be more efficient for HFB in accord with experiment. This effect is due to the greater number of low frequency vibrational modes in HFB. A correlation between the energy transfer parameters and the properties of the intramolecular potential is found. For benzene and HFB, average energies transferred per collision in the given energy range increase with energy. Besides weak collisions, more efficient ‘‘supercollisions’’ are also observed for all substrate–bath gas pairs. The histograms for vibrational energy transfer can be fitted by biexponential transition probabilities. Rotational energy transfer reveals similar trends for benzene and HFB. Cooling of rotationally hot ensembles is very efficient for both molecules. During the deactivation, the initially thermal rotational distribution heats up more strongly for argon or xenon as a collider, than for helium, leading to a quasi-steady-state in rotational energy after only a few collisions.
History
Journal
Journal of chemical physicsVolume
103Issue
2Pagination
626 - 641Publisher
AIP PublishingLocation
Melville, N.Y.Publisher DOI
ISSN
0021-9606eISSN
1089-7690Language
engPublication classification
C1.1 Refereed article in a scholarly journalCopyright notice
1995, AIPUsage metrics
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energy transferstatistical propertiesrotational energy transfer (RET)vibrational energy transfer (VET)trajectory modelscollisional energy transfer (CET)molecular dynamics (MD)quasiclassical trajectory (QCT)benzenehexafluorobenzeneScience & TechnologyPhysical SciencesChemistry, PhysicalPhysics, Atomic, Molecular & ChemicalChemistryPhysicsANISOTROPIC INTERMOLECULAR POTENTIALSHALOGENATED AROMATIC-MOLECULESVIBRATIONAL FORCE-FIELDLASER FLASH-PHOTOLYSISRANDOM-WALK MODELPOLYATOMIC-MOLECULESMACROSCOPIC DISEQUILIBRIUMSO2-AR COLLISIONSPLANE VIBRATIONSGROUND-STATE
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