The vibrational relaxation of H2. I. Experimental measurements of the rate of relaxation by H2, He, Ne, Ar, and Kr

Dove, John E.; Teitelbaum, Heshel

doi:10.1016/0301-0104(74)85027-5

Cited by 129 publications

(41 citation statements)

References 29 publications

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“…As will be seen the results depend on whether or not the molecule behaves as a classical oscillator (8 < T) during relaxation. 1, and all levels relax with rates proportional to v. If we assume a mechanism, the proportionality constant can be identified from [7]: v = 1 may relax by the T-V process with a rate constant k,,. Since the vibrational temperature is so high the population of v = 0 is much less than that at equilibrium, and the reverse process is not important.…”

Section: Relaxation Modelmentioning

confidence: 99%

“…From [4] and from [7] There are two special cases depending on whether the molecule behaves initially as a classical oscillator or not: (a) T 4 0 4 Tvi,, …”

Section: B T 4mentioning

confidence: 99%

“…The method is directly applicable to other situations. We use the Bethe-Teller law [7] for the time-dependence of the vibrational temperature: Can. J. Chem.…”

Section: Thermal Effectsmentioning

confidence: 99%

“…That this procedure appears to work for most cases has led to its acceptance. Yet [I] has really only been confirmed experimentally for a very limited range of conditions (6,7) based on the quasi-exponential decay of vibrational energy. Thus it is clear that without a complete theoretical base [ I ] must be examined more carefully.…”

Section: Introductionmentioning

confidence: 99%

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On the interpretation of vibrational relaxation times

Teitelbaum¹

1983

Can. J. Chem.

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H. TEITEI~BAUM. Can. J . Chem. 61, 1253Chem. 61, (1983 Rate laws for the evolution of vibrational energy level populations are derived when the Bcthe-Tcller law is obeyed. It is assumcd that a Boltzmann distribution is maintained via rapid V-V proccsscs. A variety of different rate laws result depending on the size and direction of the perturbation, the extent from equilibrium, and how classical the oscillator is at the initial and final conditions. An earlier analysis by Breshears is shown to be a special case. A prescription is givcn for procedures to compare relaxation times obtained from shock tube experiments and from lascr-induced tluorescence experiments, when T-V energy transfer processes are rate-determining. Corrections for thermal effects are included. Shock tube, fluorescence, and chemical activation expcrimcnts are proposed which provide meaningful conditions for testing the Bethe-Teller law and for testing the existence of a Boltzmann distribution.H. TEITELBAUM. Can. J. Chem. 61, 1253Chem. 61, (1983. On a dkduit les lois de vitesse de I'dvolution des populations du niveau d'dnergic vibrationnel lorsquc la loi de Bethe-Teller se vkrifie. On pense que la distribution de Boltzmann est maintenue par l'intermkdiaire d'un processus rapide du type V-V. 11 en rdsulte diverses lois de vitesse suivant l'amplitude et le sens de la perturbation suivant la position par rapport a I'dquilibre et suivant le comportement classique ou non de I'oscillateur dans les conditions initinles et finales. On montre qu'une analyse anterieure de Breshears n'est qu'un cas special. On dCcrit la f a~o n de proceder pour comparer les temps de relaxation obtenus Introduction In an earlier study Breshears showed that the nature and extent of the departure from equilibrium determines the relative relaxation rates of vibrational level populations ( I ) . In particular, the fluorescent intensities froin vibrational levels v decay with rate coefficients proportional to v, whereas all vibrational levels in shock wave experiments decay with the same rate coefficient. These results were shown to be natural consequences of the existence of a Boltzmann vibrational distribution and a corresponding temperature Tvib within a single mode of a harmonic oscillator. Although not clearly stated, they are also a consequence of the vibrational levels subsequently exchanging energy eVib with translational energy according to the Bethe-Teller law (2) where ET is the statistical-thermodynamic vibrational energy at the translational temperature T (which in principle also varies with time).

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Section: Relaxation Modelmentioning

confidence: 99%

“…From [4] and from [7] There are two special cases depending on whether the molecule behaves initially as a classical oscillator or not: (a) T 4 0 4 Tvi,, …”

Section: B T 4mentioning

confidence: 99%

“…The method is directly applicable to other situations. We use the Bethe-Teller law [7] for the time-dependence of the vibrational temperature: Can. J. Chem.…”

Section: Thermal Effectsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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On the interpretation of vibrational relaxation times

Teitelbaum¹

1983

Can. J. Chem.

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“…By using the state-resolved method, the DSMC calculations including the RVT energy transitions and coupled chemical reactions are carried out in various heat bath conditions. The results of rotational and vibrational temperatures and number densities obtained from the DSMC calculations are compared with the results of the master equation calculations and shock tube experimental data [9,10]. In bound-free transitions, the parameters of the existing chemical reaction models [2,[11][12][13] of the DSMC are proposed through the calibrations in the nonequilibrium heat bath conditions.…”

Section: Introductionmentioning

confidence: 99%

Rovibrational Energy Transitions and Coupled Chemical Reaction Modeling of H+H₂and He+H₂in DSMC

Kim¹

2015

International Journal of Aeronautical and Space Sciences

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A method of describing the rovibrational energy transitions and coupled chemical reactions in the direct simulation Monte Carlo (DSMC) calculations is constructed for H( 2 S)+H2(X 1 ∑g) and He( 1 S)+H2(X 1 ∑g). First, the state-specific total cross sections for each rovibrational states are proposed to describe the state-resolved elastic collisions. The state-resolved method is constructed to describe the rotational-vibrational-translational (RVT) energy transitions and coupled chemical reactions by these state-specific total cross sections and the rovibrational state-to-state transition cross sections of bound-bound and bound-free transitions. The RVT energy transitions and coupled chemical reactions are calculated by the state-resolved method in various heat bath conditions without relying on a macroscopic properties and phenomenological models of the DSMC. In nonequilibrium heat bath calculations, the state-resolved method are validated with those of the master equation calculations and the existing shock-tube experimental data. In bound-free transitions, the parameters of the existing chemical reaction models of the DSMC are proposed through the calibrations in the thermochemical nonequilibrium conditions. When the bound-free transition component of the state-resolved method is replaced by the existing chemical reaction models, the same agreement can be obtained except total collision energy model.

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Vibrational Relaxation of Diatomic Molecules in Complex Forming Collisions with Reactive Atoms

Qüack

Troe

1977

Ber Bunsenges Phys Chem

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The vibrational relaxation of H2. I. Experimental measurements of the rate of relaxation by H2, He, Ne, Ar, and Kr

Cited by 129 publications

References 29 publications

On the interpretation of vibrational relaxation times

On the interpretation of vibrational relaxation times

Rovibrational Energy Transitions and Coupled Chemical Reaction Modeling of H+H₂and He+H₂in DSMC

Vibrational Relaxation of Diatomic Molecules in Complex Forming Collisions with Reactive Atoms

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The vibrational relaxation of H2. I. Experimental measurements of the rate of relaxation by H2, He, Ne, Ar, and Kr

Cited by 129 publications

References 29 publications

On the interpretation of vibrational relaxation times

On the interpretation of vibrational relaxation times

Rovibrational Energy Transitions and Coupled Chemical Reaction Modeling of H+H2and He+H2in DSMC

Vibrational Relaxation of Diatomic Molecules in Complex Forming Collisions with Reactive Atoms

Contact Info

Product

Resources

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Rovibrational Energy Transitions and Coupled Chemical Reaction Modeling of H+H₂and He+H₂in DSMC