A quasi-classical trajectory study of the product energy partition and rovibrational distribution for the H+CD4 reaction

Rangel, Cipriano; García-Bernáldez, J. C.; Espinosa‐García, J.

doi:10.1016/j.cplett.2006.03.014

Cited by 13 publications

(15 citation statements)

References 22 publications

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“…Since a deuterium atom is transferred in this case, the tunneling effect plays a lesser role than in the H + CH 4 reaction. In 2009 our group [5] calculated the excitation function of the H + CD 4 reaction by using QCT calculations based on the CBE surface, comparing the results with the only experiment available at the time from German and coworkers [6], and previous QCT results on different PESs [2,7,8]. Experimentally, German and coworkers reported reaction cross sections only at 0.65 and 1.5 eV, finding small values at low energy which increased with the collision energy.…”

Section: Introductionmentioning

confidence: 92%

“…The initial conditions of the full dimensional QCT calculations were the same as in previous works [5,8], and so will not be repeated in this Communication. In brief, using the VENUS96 code [9], 100,000 trajectories were run for each of the four collision energies analyzed, 0.7, 1.0, 1.7, and 2.0 eV, where the maximum impact parameter, bmax, was determined for each energy.…”

Section: Computational Detailsmentioning

confidence: 98%

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On the energy-dependence of the excitation functions of the H+CH4 and H+CD4 reactions

Espinosa‐García

Corchado

2015

Computational and Theoretical Chemistry

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Section: Introductionmentioning

confidence: 92%

Section: Computational Detailsmentioning

confidence: 98%

On the energy-dependence of the excitation functions of the H+CH4 and H+CD4 reactions

Espinosa‐García

Corchado

2015

Computational and Theoretical Chemistry

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“…11 Kinetically, it reproduces the behavior of the experimental thermal rate constants and kinetic isotope effects. Dynamically, quasi-classical trajectory (QCT) calculations were performed to analyze the state-to-state dynamics of the vibrational ground-state H + CD 4 reaction, 12,13 and to analyze the role played by the C-H asymmetric stretch mode excitation of methane in the H + CH 4 reaction. 14 The reasonable agreement found with this wide variety of experimental kinetics and dynamics measurements (always qualitative, and sometimes quantitative) lends confidence to the PES-2002 polyatomic surface.…”

Section: Introductionmentioning

confidence: 99%

Quasi-Classical Trajectory Calculations Analyzing the Dynamics of the C−H Stretch Mode Excitation in the H + CHD₃ Reaction

Espinosa‐García

2007

J. Phys. Chem. A

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A state-to-state dynamics study was performed at a collision energy of 1.53 eV to analyze the effect of the C-H stretch mode excitation on the dynamics of the gas-phase H+CHD3 reaction, which can evolve along two channels, H-abstraction, CD3+H2, and D-abstraction, CHD2+HD. Quasi-classical trajectory calculations were performed on an analytical potential energy surface constructed previously by our group. First, strong coupling between different vibrational modes in the entry channel was observed; i.e., the reaction is non-adiabatic. Second, we found that the C-H stretch mode excitation has little influence on the product rotational distributions for both channels, and on the vibrational distribution for the CD3+H2 channel. However, it has significant influence on the product vibrational distribution for the CHD2+HD channel, where the C-H stretch excitation is maintained in the products, i.e., the reaction shows mode selectivity, reproducing the experimental evidence. Third, the C-H stretch excitation by one quantum increases the reactivity of the vibrational ground-state, in agreement with experiment. Fourth, the state-to-state angular distributions of the CD3 and CHD2 products are reported, finding that for the reactant ground-state the products are practically sideways, whereas the C-H excitation yields a more forward scattering.

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“…CD 3 þ HD reaction have been carried out [6][7][8]. Recently, the energy distributions of the products for the H þ CD 4 !…”

Section: Introductionmentioning

confidence: 99%

“…Recently, the energy distributions of the products for the H þ CD 4 ! CD 3 þ HD reaction were investigated by Hu et al [6] and Espinosa-Garcia and coworkers [8] using QCT calculations on different PESs: (1) a DFT surface at the B3LYP/ 6-31G** level; (2) two semiempirical surfaces, MSINDO, and reparametrized MSINDO; and (3) an empirical surface developed by Espinosa-Garcia (EG). They found that 24 and 20% of the total available energy are released into the vibrational energy and rotational energy of the HD product on the DFT surface, suggesting a vibrationally and rotationally much hotter HD product, in strong contrast with the experimental results.…”

Section: Introductionmentioning

confidence: 99%

Direct MP2 molecular dynamics studies of H atom reaction with CD₄ and CH₄

Lü

Kuang

et al. 2011

Int J of Quantum Chemistry

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ABSTRACT:The mechanism and dynamics of the H þ CD 4 ! CD 3 þ HD (I) and H þ CH 4 ! CH 3 þ H 2 (II) reactions have been investigated by electronic structure methods. The minimum-energy path and vibrational frequencies along the intrinsic reaction coordinate are calculated at MP2/cc-pVDZ level. Energy distributions of the products are also obtained by the direct classical trajectory calculations at the MP2/ cc-pVDZ level. It is found that most of the available energy appears as product translational energy, and very little of the available energy is partitioned into internal excitation of the HD (H 2 ) product for reaction I (II), which is in agreement with the experimental evidence. The results indicate that the experimental results could be reproduced by the direct MP2 molecular dynamics calculations. The rotational state distributions of the products show the HD (H 2 ) products are formed with lower rotational quantum numbers than the CD 3 (CH 3 ) products.

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A quasi-classical trajectory study of the product energy partition and rovibrational distribution for the H+CD4 reaction

Cited by 13 publications

References 22 publications

On the energy-dependence of the excitation functions of the H+CH4 and H+CD4 reactions

On the energy-dependence of the excitation functions of the H+CH4 and H+CD4 reactions

Quasi-Classical Trajectory Calculations Analyzing the Dynamics of the C−H Stretch Mode Excitation in the H + CHD₃ Reaction

Direct MP2 molecular dynamics studies of H atom reaction with CD₄ and CH₄

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A quasi-classical trajectory study of the product energy partition and rovibrational distribution for the H+CD4 reaction

Cited by 13 publications

References 22 publications

On the energy-dependence of the excitation functions of the H+CH4 and H+CD4 reactions

On the energy-dependence of the excitation functions of the H+CH4 and H+CD4 reactions

Quasi-Classical Trajectory Calculations Analyzing the Dynamics of the C−H Stretch Mode Excitation in the H + CHD3 Reaction

Direct MP2 molecular dynamics studies of H atom reaction with CD4 and CH4

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Product

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Quasi-Classical Trajectory Calculations Analyzing the Dynamics of the C−H Stretch Mode Excitation in the H + CHD₃ Reaction

Direct MP2 molecular dynamics studies of H atom reaction with CD₄ and CH₄