Correlated Dynamics of the O(3P) + CHD3(v=0) Reaction: A Joint Crossed-Beam and Quasiclassical Trajectory Study

Zhang, Bailin; Liu, Kopin; Czakó, Gábor

doi:10.1021/jp510377k

Cited by 14 publications

(18 citation statements)

References 49 publications

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“…A similar theoretical/experimental controversy was also reported recently by Zhang et al for the O( 3 P) + CHD 3 ( v 1 =0) reaction. Whereas the OH + CD 3 channel is preferred (i.e., OD/OH ratio < 1) experimentally, theoretically, the other channel, OD + CHD 2 , is preferred (i.e., OD/OH ratio > 1).…”

Section: Resultssupporting

confidence: 84%

“…(Note that the PES-2014 barrier better reproduces the benchmark classical barrier for this reaction, 41 4925 cm −1 ). Zhang et al 40 concluded that the discrepancy arises most likely from experiment, although the fact that the physical quantities measured in the two cases are different cannot be ruled out. The recent QCT calculations based on PES-2014 seem to confirm this finding.…”

Section: Resultsmentioning

confidence: 99%

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Quasiclassical Trajectory Study on the Role of CH-Stretching Vibrational Excitation in the F(²P) + CHD₃(v₁=0,1) Reactions

Espinosa‐García

2015

J. Phys. Chem. A

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To analyze the role of CH-stretching vibrational excitation on the reactivity and dynamics of the F((2)P) + CHD3(v1=0,1) reactions, quasiclassical trajectory calculations using a full-dimensional analytical potential energy surface at different collision energies were performed. The extra energy of the CH excitation had almost no effect on the reactivity for the DF + CHD2 channel, although it increased the reactivity for the HF + CD3 channel, with the net effect being that CH excitation barely modified overall reactivity. In addition, the DF/HF branching ratio was not far from the statistical value for the ground-state reaction, whereas CH excitation decreased this ratio. These results, intimately related to the topology of the entrance channel, agree with recent theoretical results obtained using different surfaces (although some differences even persist among them) but strongly contradict recent experiments. This controversy will doubtless guarantee more accurate experiments and theoretical calculations in the future. However, properties related to the exit channel show reasonable theoretical/experimental agreement. Thus, the extra energy of CH excitation is mainly channelled into the HF and DF products for the HF + CD3 and DF + CHD 2 channels, respectively, and the product scattering distributions are forward in both channels, where CH excitation has almost no effect on them.

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Section: Resultssupporting

confidence: 84%

Section: Resultsmentioning

confidence: 99%

Quasiclassical Trajectory Study on the Role of CH-Stretching Vibrational Excitation in the F(²P) + CHD₃(v₁=0,1) Reactions

Espinosa‐García

2015

J. Phys. Chem. A

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“…Zhang et al studied this reaction at a hyperthermal collision energy of 64 kcal/mol and found that the OH product was scattered in the forward direction, which showed a stripping mechanism. However, with extended collision energies ranging from 7.5 to 13.5 kcal/mol, Zhang and co-workers revealed that the product angular distributions were backward scattered for the O( 3 P) + CHD 3 reaction, which indicated a direct rebound mechanism. Zhang and Liu investigated the effect of the bending excitation of methane on the title reaction and found that the bend-excited methane yielded more vibrational excitation of the hydroxyl coproduct.…”

Section: Introductionmentioning

confidence: 99%

Thermal Rate Constants for the O(³P) + CH₄→ OH + CH₃Reaction: The Effects of Quantum Tunneling and Potential Energy Barrier Shape

Zhao

2016

J. Phys. Chem. A

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The rate constants and kinetic isotope effects for the O(P) + CH reaction have been investigated with the quantum instanton method in full dimensionality. The calculated rate constants are in good agreement with the experimental values above 400 K, below which the measured values are scattered. Compared to other theoretical approaches, the quantum instanton method predicts the largest quantum tunneling effect, so it gives the largest rate constants at low temperatures. The calculated kinetic isotope effects are always much larger than 1 and increase with decreasing temperature, due to the zero-point energy and quantum tunneling. Our calculations on different potential energy surfaces demonstrate that the potential energy barrier shape dominates the magnitude of quantum tunneling and has a great effect on the kinetic isotope effect.

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“…Note that theoretical pair-correlated speed distributions have rarely been published for polyatomic reactions (see ref. [24] for a recent example in the case of O+CHD 3 ).…”

Section: B Pair-correlated Speed Distributionmentioning

confidence: 99%

Pair-correlated speed distributions for the OH+CH4/CD4 reactions: Further remarks on their classical trajectory calculations in a quantum spirit

Bonnet

Corchado

Espinosa‐García

2016

Comptes Rendus. Chimie

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Ten years ago, Liu and co-workers measured pair-correlated product speed and angular distributions for the OH+CH4/CD4 reactions at the collision energy of ∼ 10 kcal/mol [A 2005, 109, 8989]. Recently, two of us could semi-quantitatively reproduce these measurements by performing full-dimensional classical trajectory calculations in a quantum spirit on an ab-initio potential energy surface of their own [J. Espinosa-Garcia and J. C. Corchado, Theor Chem Acc, 2015, 134, 6 ; J. Phys. Chem. B, Article ASAP, DOI: 10.1021/acs.jpcb.5b04290]. The goal of the present work is to show that these calculations can be significantly improved by adding a few more constraints to better comply with the experimental conditions. Overall, the level of agreement between theory and experiment is remarkable considering the large dimensionality of the processes under scrutiny.

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Correlated Dynamics of the O(³P) + CHD₃(v=0) Reaction: A Joint Crossed-Beam and Quasiclassical Trajectory Study

Cited by 14 publications

References 49 publications

Quasiclassical Trajectory Study on the Role of CH-Stretching Vibrational Excitation in the F(²P) + CHD₃(v₁=0,1) Reactions

Quasiclassical Trajectory Study on the Role of CH-Stretching Vibrational Excitation in the F(²P) + CHD₃(v₁=0,1) Reactions

Thermal Rate Constants for the O(³P) + CH₄→ OH + CH₃Reaction: The Effects of Quantum Tunneling and Potential Energy Barrier Shape

Pair-correlated speed distributions for the OH+CH4/CD4 reactions: Further remarks on their classical trajectory calculations in a quantum spirit

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Correlated Dynamics of the O(3P) + CHD3(v=0) Reaction: A Joint Crossed-Beam and Quasiclassical Trajectory Study

Cited by 14 publications

References 49 publications

Quasiclassical Trajectory Study on the Role of CH-Stretching Vibrational Excitation in the F(2P) + CHD3(v1=0,1) Reactions

Quasiclassical Trajectory Study on the Role of CH-Stretching Vibrational Excitation in the F(2P) + CHD3(v1=0,1) Reactions

Thermal Rate Constants for the O(3P) + CH4→ OH + CH3Reaction: The Effects of Quantum Tunneling and Potential Energy Barrier Shape

Pair-correlated speed distributions for the OH+CH4/CD4 reactions: Further remarks on their classical trajectory calculations in a quantum spirit

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Correlated Dynamics of the O(³P) + CHD₃(v=0) Reaction: A Joint Crossed-Beam and Quasiclassical Trajectory Study

Quasiclassical Trajectory Study on the Role of CH-Stretching Vibrational Excitation in the F(²P) + CHD₃(v₁=0,1) Reactions

Quasiclassical Trajectory Study on the Role of CH-Stretching Vibrational Excitation in the F(²P) + CHD₃(v₁=0,1) Reactions

Thermal Rate Constants for the O(³P) + CH₄→ OH + CH₃Reaction: The Effects of Quantum Tunneling and Potential Energy Barrier Shape