Energy-dependent collisional deactivation of vibrationally excited azulene

Shi, Junbo; Barker, John R.

doi:10.1063/1.454460

Cited by 100 publications

(65 citation statements)

References 34 publications

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“…On the other hand, there is a large discrepancy to the (AE)-values determined in direct experiments, where amounts between -92 cm-' and -175 cm-l are given for collisions of H2 with various excited hydrocarbon molecules [23,24]. With these values, our calculations lead to a D/S between 25 and about 7, respectively, which is much too large compared with our experiments.…”

Section: Resultscontrasting

confidence: 74%

“…A possible change here would have a considerable influence on the ratio Dz/Di. This problem is still under discussion today [24,25], and as long as such influences are not to be taken into account exactly, there appears to be little reason in a more elaborated treatment of the collisional transition probabilities as well as of the microcanonical rate constants. The flat steady-state distribution of the chemically activated butane is influenced only to a very little extend by high pressures and/or large (AE)-values and in each case extends to energies above the threshold, in this way maintaining the reaction path, which contributes to Dz.…”

Section: Resultsmentioning

confidence: 97%

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An extended mechanism for chemical activation systems

Olzmann

Gebhardt

Scherzer

1991

Int J of Chemical Kinetics

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The classical mechanism of chemically activated unimolecular reactions is extended to interpret experimental results in systems olefin/hydrogen atoms. In the case of a large excess of the latter, one has to take into consideration a second chemical activation of the primarily formed radicals by their recombination with H-atoms to yield chemically activated alkane molecules. The radicals as well as the alkane molecules may decompose, and a method based on the coupling of two steady-state master equations is developed to evaluate the contribution of either of the two reaction paths to the ratio decomposition to stabilization. The treatment proposed is demonstrated for the example cis but-a-ene/excess of thermal hydrogen atoms in the presence of molecular hydrogen as a bath gas at 298 K. It turns out that the step via activated butane is not negligible under these conditions.

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Section: Resultscontrasting

confidence: 74%

Section: Resultsmentioning

confidence: 97%

An extended mechanism for chemical activation systems

Olzmann

Gebhardt

Scherzer

1991

Int J of Chemical Kinetics

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“…It can be seen again that the accord between trajectory data and BR W model B predictions is very good for the heavier bath gases, but that the dynamical approximations in the BRW model B result in a great underestimate of the energy transfer for the lightest bath gases (He and Ne). This underestimate probably arises because the lightest bath gases are more likely to bounce off the substrate after the first (few) atom-atom encounters and, hence, re- [27][28][29] and of the Gottingen group (Refs. 30 and 31) 1 using method described in text.…”

Section: Onehas/(et) And/(e't)mentioning

confidence: 99%

“…[27][28][29] These experiments measure (I1E) (or ratherinfer the values of RE',I after calibration), but the values of (I1E) can be converted with minimal uncertainty to equivalent values of (I1E 2) 1/2 through Fig. 4.…”

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confidence: 99%

Collisional energy transfer in highly excited molecules: Calculations of the dependence on temperature and internal, rotational, and translational energy

Clarke

Oref

Gilbert

et al. 1992

The Journal of Chemical Physics

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Translational and rotational excitation of the CO 2 (00 0 0) vibrationless state in the collisional quenching of highly vibrationally excited perfluorobenzene: Evidence for impulsive collisions accompanied by large energy transfers J. Chem. Phys. 106, 7055 (1997) Classical trajectory calculations of the rate of collisional energy transfer between a bath gas and a highly excited polyatomic method, and the average energy transferred per collision, as functions of the bath gas translational energy and temperature, are reported. The method used is that of Lim and Gilbert [J. Phys. Chem. 94, 72 (1990)], which requires only about 500 trajectories for convergence, and generates extensive data on the collisional energy transfer between Xe and azulene, as a function of temperature, initial relative translational energy (E T)' and azulene initial internal energy (E'). The observed behavior can be explained qualitatively in terms of the Xe interacting in a chattering collision with a few substrate atoms, with the collision duration being much too brief to permit ergodicity but with a general tendency to transfer energy from hotter to colder modes (both internal and translational). At thermal energies, trajectory and experimental data show that the root-mean-squared energy transfer per collision, (ali 2) 112, is relatively less dependent on E' than the mean energy transfer (ali). The calculated temperature dependence is weak: (AE 2) 112 0:: To. ,corresponding to (AE down ) 0:: To.23 • Values for the calculated average rotational energy transferred per collision (data currently only available from trajectories, and required for falloff calculations for radical-radical and ion-molecule reactions) are of the order of k B T, and similar to those for the internal energy; there is extensive collision-induced internal-rotational energy transfer. The biased random walk "model B," as discussed in text, is found to be in accord with much of the trajectory data and with experiment. This suggests that energy transfer is through pseudorandom mUltiple interactions between the bath gas and a few reactant atoms; the "kick" given by the force at the turning point of each atom-atom encounter governs the amount of energy transferred. Moreover, a highly simplified version of this model explains why average energies transferred per collision for simple bath gases have the order-of-magnitude values seen experimentally, an explanation which has not been provided hitherto.

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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] Molecules highly excited to near their dissociation threshold can undergo bond dissociation and vibrational relaxation, processes that play an important role in reaction dynamics. Most of experimental studies have been carried out using time-resolved infrared flourescence (TR-IRF) [2][3][4] or ultraviolet absorption (UVA). [5][6][7][8] Several studies have been employed by techniques based on photothermal processes.…”

Section: Introductionmentioning

confidence: 99%

Energy Flow and Bond Dissociation of Vibrationally Excited Toluene in Collisions with N₂and O₂

Ree

Kim²,

Lee

2013

Bulletin of the Korean Chemical Society

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Energy flow and C-H methyl and C-H ring bond dissociations in vibrationally excited toluene in the collision with N 2 and O 2 have been studied by use of classical trajectory procedures. The energy lost by the vibrationally excited toluene upon collision is not large and it increases slowly with increasing total vibrational energy content between 5,000 and 45,000 cm −1 . Intermolecular energy transfer occurs via both of V-T and V-V transfers. Both of V-T and V-V transfers increase as the total vibrational energy of toluene increases. When the total energy content E T of toluene is sufficiently high, either C-H bond can dissociate. The C-H methyl dissociation probability is higher than the C-H ring dissociation probability, and that in the collision with N 2 is larger than with O 2 .

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Energy-dependent collisional deactivation of vibrationally excited azulene

Cited by 100 publications

References 34 publications

An extended mechanism for chemical activation systems

An extended mechanism for chemical activation systems

Collisional energy transfer in highly excited molecules: Calculations of the dependence on temperature and internal, rotational, and translational energy

Energy Flow and Bond Dissociation of Vibrationally Excited Toluene in Collisions with N₂and O₂

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Energy-dependent collisional deactivation of vibrationally excited azulene

Cited by 100 publications

References 34 publications

An extended mechanism for chemical activation systems

An extended mechanism for chemical activation systems

Collisional energy transfer in highly excited molecules: Calculations of the dependence on temperature and internal, rotational, and translational energy

Energy Flow and Bond Dissociation of Vibrationally Excited Toluene in Collisions with N2and O2

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Energy Flow and Bond Dissociation of Vibrationally Excited Toluene in Collisions with N₂and O₂