Orientation dependence for Br formation in the reaction of oriented OH radical with HBr molecule

Tsai, Po‐Yu; Che, Dock‐Chil; Nakamura, Masaaki; Lin, King‐Chuen; Kasai, Toshio

doi:10.1039/c0cp01089h

Cited by 31 publications

(35 citation statements)

References 36 publications

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“…This means the favorite route of this reaction is the two reactants enter the entrance vdW minimum to form HOHBr, then scale the transition state to make the reaction occur. This has been confirmed by the crossed beam scattering experiment1718 by Tsai et al . They found the orientation dependence for the title reaction that the reaction is favored by OH re-orientating its O-end to face the HBr.…”

Section: Resultssupporting

confidence: 59%

“…This indirectly proves Tsai et al . molecular beam study1718 that Br formation of this reaction has orientation dependence which favors the O-end attack. On one hand, the faster rotation of HBr will make H in HBr cannot attack O-end easily; on the other hand, the faster rotation of OH will make O-end having difficulty to receive the H in HBr.…”

Section: Resultsmentioning

confidence: 99%

“…observed the negative collision energy dependence of reaction cross section for the HBr + OH/OD reaction in a crossed molecular beam experiment. Tsai et al 1718. reported the orientation dependence of the Br formation and found that O-end attack is more favored for this reaction.…”

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confidence: 99%

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Quantum dynamics study of energy requirement on reactivity for the HBr + OH reaction with a negative-energy barrier

Wang

2017

Sci Rep

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A time-dependent, quantum reaction dynamics approach in full dimensional, six degrees of freedom was carried out to study the energy requirement on reactivity for the HBr + OH reaction with an early, negative energy barrier. The calculation shows both the HBr and OH vibrational excitations enhance the reactivity. However, even this reaction has a negative energy barrier, the calculation shows not all forms of energy are equally effective in promoting the reactivity. On the basis of equal amount of total energy, the vibrational energies of both the HBr and OH are more effective in enhancing the reactivity than the translational energy, whereas the rotational excitations of both the HBr and OH hinder the reactivity. The rate constants were also calculated for the temperature range between 5 to 500 K. The quantal rate constants have a better slope agreement with the experimental data than quasi-classical trajectory results.

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Section: Resultssupporting

confidence: 59%

Section: Resultsmentioning

confidence: 99%

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Quantum dynamics study of energy requirement on reactivity for the HBr + OH reaction with a negative-energy barrier

Wang

2017

Sci Rep

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“…Recently, quantum chemical calculations of an accurate global potential energy surface 8 and extensive classical trajectory simulations 9 reproduced the behavior, while a review 10 pointed out at existing evidence from molecular beam scattering experiments with oriented reactants 11,12 of the key role of stereodynamics, establishing the ground for a mechanistic interpretation.…”

Section: Table Of Contents (Toc)mentioning

confidence: 93%

Stereodynamical Origin of Anti-Arrhenius Kinetics: Negative Activation Energy and Roaming for a Four-Atom Reaction

Coutinho

Silva

Oliveira

et al. 2015

J. Phys. Chem. Lett.

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The OH + HBr → H2O + Br reaction, prototypical of halogen-atom liberating processes relevant to mechanisms for atmospheric ozone destruction, attracted frequent attention of experimental chemical kinetics: the nature of the unusual reactivity drop from low to high temperatures eluded a variety of theoretical efforts, ranking this one among the most studied four-atom reactions. Here, inspired by oriented molecular-beams experiments, we develop a first-principles stereodynamical approach. Thermalized sets of trajectories, evolving on a multidimensional potential energy surface quantum mechanically generated on-the-fly, provide a map of most visited regions at each temperature. Visualizations of rearrangements of bonds along trajectories and of the role of specific angles of reactants' mutual approach elucidate the mechanistic change from the low kinetic energy regime (where incident reactants reorient to find the propitious alignment leading to reaction) to high temperature (where speed hinders adjustment of directionality and roaming delays reactivity).

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“…Several methods have been proposed to control the molecular orientation by external fields and/or by collisions in supersonic seeded expansions (see for instance Refs. [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23]). …”

Section: Introductionmentioning

confidence: 99%

Polar molecules engaged in pendular states captured by molecular-beam scattering experiments

et al. 2014

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We demonstrate that when two polar molecules as those of water, ammonia, and hydrogen sulfide encounter each other at a distance much larger than their dimensions they engage a synchronous motion that promotes the transformation of free rotations into coupled pendular states. This discovery has been prompted by high-resolution molecular beam scattering experiments presented here, addressed to the measure of the total integral cross section changes as a consequence of molecular rotation couplings. The experimental observations and the theoretical treatment developed to shed light on the details of the phenomenon suggest that the interplay among free rotations and pendular states depends on the relative velocity, on the rotational levels, and on the dipole moments of the interacting molecules. The features of this intriguing phenomenon may be crucial for the interpretation and the control of basic chemical and biological processes.

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Orientation dependence for Br formation in the reaction of oriented OH radical with HBr molecule

Cited by 31 publications

References 36 publications

Quantum dynamics study of energy requirement on reactivity for the HBr + OH reaction with a negative-energy barrier

Quantum dynamics study of energy requirement on reactivity for the HBr + OH reaction with a negative-energy barrier

Stereodynamical Origin of Anti-Arrhenius Kinetics: Negative Activation Energy and Roaming for a Four-Atom Reaction

Polar molecules engaged in pendular states captured by molecular-beam scattering experiments

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