The influence of translational and vibrational energy on the reaction of Cl with CH3D

Berke, Andrew E.; Volpa, Ethan H.; Annesley, Christopher J.; Crim, F. Fleming

doi:10.1063/1.4808378

Cited by 12 publications

(8 citation statements)

References 44 publications

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“…Specifically, the reactivity increase with J and lower K values yield higher reactivity within a J manifold. Similar rotational enhancement, albeit qualitatively, has also been observed in the reaction of Cl with CH 3 D. 75 In view of the smallness of the rotational energy (merely ∼20 cm −1 for J = 2), such a profound enhancement in reactivity is quite remarkable. A slightly higher, albeit subtle, efficacy in rateenhancement for JK = 10 than 1 ±1 is noted.…”

Section: Resultsmentioning

confidence: 69%

Rotational mode specificity in the Cl + CHD3 → HCl + CD3 reaction

Wang

Jiang

et al. 2014

The Journal of Chemical Physics

109

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By exciting the rotational modes of vibrationally excited CHD3(v1 = 1, JK), the reactivity for the Cl + CHD3 → HCl + CD3 reaction is observed enhanced by as much as a factor of two relative to the rotationless reactant. To understand the mode specificity, the reaction dynamics was studied using both a reduced-dimensional quantum dynamical model and the conventional quasi-classical trajectory method, both of which reproduced qualitatively the measured enhancements. The mechanism of enhancement was analyzed using a Franck-Condon model and by inspecting trajectories. It is shown that the higher reactivity for higher J states of CHD3 with K = 0 can be attributed to the enlargement of the cone of acceptance. On the other hand, the less pronounced enhancement for the higher J = K states is apparently due to the fact that the rotation along the C-H bond is less effective in opening up the cone of acceptance.

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Section: Resultsmentioning

confidence: 69%

Rotational mode specificity in the Cl + CHD3 → HCl + CD3 reaction

Wang

Jiang

et al. 2014

The Journal of Chemical Physics

109

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“…Under isolated reactive collision conditions, these reactions exemplify bond-specific chemistry, vibrational modespecific dynamics, the effects of the impact parameter on scattering, and the ways in which post-TS complexes can influence product energy disposal (79)(80)(81)(82)(83)(84)(85). In recent work on reactions of Cl atoms with alkenes, Suits and coworkers (86)(87)(88) and Preston et al (89) examined competition between two pathways for HCl production: direct H atom abstraction and reaction mediated by the addition of a Cl atom to the C=C bond.…”

Section: Atom Reactions With Organic Solutesmentioning

confidence: 99%

Dynamics of Bimolecular Reactions in Solution

Orr-Ewing

2015

Annu. Rev. Phys. Chem.

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Mechanisms of bimolecular chemical reactions in solution are amenable to study on picosecond timescales, both by transient absorption spectroscopy and by computer simulation. The dynamics of exothermic reactions of CN radicals and of Cl and F atoms with organic solutes in commonly used solvents are contrasted with the corresponding dynamics in the gas phase. Many characteristics of the gas-phase reaction dynamics persist in solution, such as efficient energy release to specific vibrational modes of the products. However, additional complexities associated with the presence of the solvent are open to investigation. These features of liquid-phase reactions include the role of solvent-solute complexes, solvent caging, coupling of the product motions to the solvent bath, thermalization of internally excited reaction products, incipient hydrogen bond formation, and involvement of charge-separated states that arise from proton transfer.

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“…Control of chemical reactions is a central issue of chemistry. − A simple means of controlling the outcome of a bimolecular reaction is exciting motion along the reaction coordinate that drives the reactants into the desired products. Thanks to the advent of laser techniques, selectively exciting a reactant vibrational mode or a chemical bond in some bimolecular reactions has become feasible. − ,− When the excited vibrational mode or bond of reactants maps significantly onto the reaction coordinate and the retention of that excitation long enough, the reactivity will be significantly enhanced.…”

Section: Introductionmentioning

confidence: 99%

Mode- and Bond-Selected Reaction of H with Local Mode Molecule HDS

et al. 2020

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Understanding mode- and bond-selected dynamics of elementary chemical reactions is of central importance in molecular reaction dynamics. The initial state-selected time-dependent wave packet method is employed to study the mode and bond selectivity, isotopic branching ratio, and temperature dependence of rate constants of the two-channel reaction of H with local mode molecule HDS. For the abstraction channel, fundamental excitation of the HS (DS) bond of the reactant HDS significantly enhances the H-abstraction (D-abstraction) reaction, whose efficacy is higher than the same amount of translational energy except at low energies just above the energy threshold. This is in sharp contrast to the prediction of Polanyi rules: translational energy is more efficient than vibrational energy in enhancing a reaction with an early barrier. The recent sudden vector projection model is then applied to rationalize the observed mode specificity, which, however, shows that the translational mode vector has a larger coupling with the reaction coordinate than the stretching vector of the active bond, implying a reversed relative efficacy on promoting the reaction as well. In contrast, the mode and bond specificity for the exchange channel is not as strong as for the abstraction channel due to the regulation of the shallow well along the reaction path.

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The influence of translational and vibrational energy on the reaction of Cl with CH3D

Cited by 12 publications

References 44 publications

Rotational mode specificity in the Cl + CHD3 → HCl + CD3 reaction

Rotational mode specificity in the Cl + CHD3 → HCl + CD3 reaction

Dynamics of Bimolecular Reactions in Solution

Mode- and Bond-Selected Reaction of H with Local Mode Molecule HDS

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