Theoretical and experimental revision of the water bending excitation in the OH/OD + GeH4 reactions

Espinosa‐García, J.; Corchado, J. C.; Butkovskaya, N. I.; Setser, D. W.

doi:10.1007/s00214-019-2506-2

Cited by 5 publications

(4 citation statements)

References 12 publications

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“…One interesting aspect of vibrational energy distributions for H 2 O and DO─H products from H‐atom abstraction is the dynamics associated with excitation of the bending mode 9,13,45,46 . Espinosa and coworkers 9,45 have illustrated that bending excitation can depend on subtle properties of the potential energy surface. It should be noted that the QCT calculations usually give distributions for stretching and bending excitation that are too narrow relative to the experimental based distributions.…”

Section: Discussionmentioning

confidence: 99%

Reactions of OH and OD radicals with simple thiols and sulfides studied by infrared chemiluminescence of isotopic water products: Reaction OH + CH₃SH revisited

Butkovskaya

Setser

2021

Int J of Chemical Kinetics

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Vibrational excitation of the H2O, HOD, and D2O product molecules from the reactions of OH and OD radicals with CH3SH, CH3C(O)SH, (CH3)3CSH, H2S, and CH3SCH3 was determined by modeling the infrared emission spectra using a renovated and extended set of model spectroscopic bands. Using the deuterated reactant, CH3SD, it was possible to separate spectra of abstraction from C‐ and S‐sites, which allowed measurement of branching fractions and kinetic isotope effects for individual channels. For the OH + CH3SH reaction, branching fractions of 0.13 ± 0.03 (C─H) and 0.87 ± 0.03 (S─H) were obtained. The vibrational energy released to water from abstraction of H‐atoms from the C─H and S─H sites of the reactant molecules is described. The results reported in this paper take precedence over an earlier study of CH3SH. The vibrational energy partitioning between the stretch and bend modes of water molecules from the reactions of the thiols and related reactions of H2S and CH3SCH3 are discussed. The mechanism for the OH + CH3SSCH3 reaction was confirmed to be addition followed mainly by decomposition to CH3SH and CH3SO.

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Section: Discussionmentioning

confidence: 99%

Reactions of OH and OD radicals with simple thiols and sulfides studied by infrared chemiluminescence of isotopic water products: Reaction OH + CH₃SH revisited

Butkovskaya

Setser

2021

Int J of Chemical Kinetics

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“…These findings represent a direct extension of Polanyi's rules to polyatomic reactions. However, when dealing with “central” barriers, we found contradictory results [11,12] . For instance, in the O( 3 P)+CH 4 reaction, translational energy proves to be more effective than vibrational energy, whereas the opposite trend was observed in the H+C 2 H 6 reaction.…”

Section: Introductionmentioning

confidence: 89%

“…[16]), there remains a notable scarcity of both theoretical and experimental information regarding reactions involving ethane. In order to delve deeper into this realm, we began by studying a series of ethane reactions [12,17] H+C 2 H 6 and Cl( 2 P)+C 2 H 6 , both featuring a “central” barrier. While the chlorine reaction shows near‐similar reactivity enhancement by vibrational and translational energies, our findings in the hydrogen reaction reveal that at lower collision energies, translational energy proves to be more effective than vibrational energy, while at higher collision energies, the opposite holds true‐vibrational energy has greater effectiveness, validating Liu′s previous conclusions for methane reactions [16] .…”

Section: Introductionmentioning

confidence: 99%

Role of the Vibrational and Translational Energies in the CN(v)+C₂H₆(ν₁, ν₂, ν₅ and ν₉) Reactions. A Theoretical QCT Study

Espinosa‐Garcia,

Rangel,

Corchado

2024

ChemPhysChem

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Quasi‐classical trajectory (QCT) calculations were conducted to analyse the influence of vibrational versus translational energy in promoting reactivity, and the impact of vibrational excitation. The investigation revealed that independent vibrational excitation of ethane’s symmetric and asymmetric stretching modes (differing by only 15 cm‑1) yielded comparable reaction cross‐sections, HCN(v) vibrational product distributions, and scattering distributions. This observation dismisses any significant mode selectivity. Moreover, an equivalent amount of energy provided as translational energy gave rise to slightly lower reactivity compared to the same amount of energy provided as vibrational energy. This effect is more evident at low energies, presenting a counterintuitive scenario in an ‘early transition state’ reaction. These findings challenge the application of Polanyi's rules in polyatomic systems. Our calculations reveal that the reaction cross‐section remains practically unaffected by CN vibrational excitation, suggesting that the CN stretching is a spectator mode. The results were rationalized by considering the coupling between different vibrational modes, between vibrational modes and the reaction coordinate, and a significant vibrational energy redistribution before collision, that creates an unphysical energy flow, resulting in loss of adiabaticity and vibrational memory before the reactants’ collision. These theoretical findings require future confirmation through experimental or theoretical quantum mechanical studies.

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“…Theoretically, using either quasi-classical trajectories (QCT) or quantum dynamics (QD) on full-dimensional accurate potential energy surfaces (PESs), ample investigations have been carried out on the mode-specific chemistry in various chemical reactions, such as H/O/F/Cl/OH + H 2 O/ CH 4 (and their isotopologs) , OH/OD + GeH 4 [33], Cl + C 2 H 6 [34,35], OH + HO 2 [36], the SN 2 reactions F − + CH 3 Cl [37,38] and F − + CH 3 I [39], H + NH 3 [40], H + H 2 S [41][42][43]. Based on ample studies of atom-diatom reactions, Polanyi summarized that: for exothermic reactions with an "early barrier," the translation motion is more effective to enhance the reactivity than the vibrational motion, whereas the reactant vibration would be more effective for endothermic reactions with a "late barrier" [44,45].…”

Section: Introductionmentioning

confidence: 99%

Mode specificity of a multi-channel reaction prototype: F + CH3OH → HF + CH3O/CH2OH

Lü

2020

Theor Chem Acc

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Mode-specific chemistry has been a hot research topic in the field of molecular reaction dynamics since different degrees of freedom play potentially divergent effects on the reactivity of different channels and the associated product branching ratios. In this work, we examine the mode specificity effect in the reaction F + CH 3 OH → HF + CH 3 O (R1)/CH 2 OH (R2), a prototypical polyatomic reaction with multiple channels and submerged barriers, by extensive vibrational state-specific molecular dynamical calculations with the quasi-classical trajectory approach on a globally accurate full-dimensional potential energy surface. Complicated mode specificity effects are revealed. In particular, the vibrational excitations of the O-H stretching motion and the torsional motion with respect to the C-O axis can enhance the reactivity of R1 significantly. The excitations of the C-H stretching vibrational motions do not influence R1. For another channel, R2, the C-H stretching vibrational excitation shows some weak enhancement effect, while the O-H stretching vibrational excitation shows no effect on the reactivity. Then, the sudden vector projection model is employed to rationalize the mode specificity effects and understand the product energy partitioning in the two channels. The ro-vibrational state distributions of the nascent product HF/DF from F + CH 3 OH/CH 3 OD/CD 3 OH/CD 3 OD are also in good agreement with available experiments.

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Theoretical and experimental revision of the water bending excitation in the OH/OD + GeH4 reactions

Cited by 5 publications

References 12 publications

Reactions of OH and OD radicals with simple thiols and sulfides studied by infrared chemiluminescence of isotopic water products: Reaction OH + CH₃SH revisited

Reactions of OH and OD radicals with simple thiols and sulfides studied by infrared chemiluminescence of isotopic water products: Reaction OH + CH₃SH revisited

Role of the Vibrational and Translational Energies in the CN(v)+C₂H₆(ν₁, ν₂, ν₅ and ν₉) Reactions. A Theoretical QCT Study

Mode specificity of a multi-channel reaction prototype: F + CH3OH → HF + CH3O/CH2OH

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Theoretical and experimental revision of the water bending excitation in the OH/OD + GeH4 reactions

Cited by 5 publications

References 12 publications

Reactions of OH and OD radicals with simple thiols and sulfides studied by infrared chemiluminescence of isotopic water products: Reaction OH + CH3SH revisited

Reactions of OH and OD radicals with simple thiols and sulfides studied by infrared chemiluminescence of isotopic water products: Reaction OH + CH3SH revisited

Role of the Vibrational and Translational Energies in the CN(v)+C2H6(ν1, ν2, ν5 and ν9) Reactions. A Theoretical QCT Study

Mode specificity of a multi-channel reaction prototype: F + CH3OH → HF + CH3O/CH2OH

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Reactions of OH and OD radicals with simple thiols and sulfides studied by infrared chemiluminescence of isotopic water products: Reaction OH + CH₃SH revisited

Reactions of OH and OD radicals with simple thiols and sulfides studied by infrared chemiluminescence of isotopic water products: Reaction OH + CH₃SH revisited

Role of the Vibrational and Translational Energies in the CN(v)+C₂H₆(ν₁, ν₂, ν₅ and ν₉) Reactions. A Theoretical QCT Study