Imaging O(3P)+alkane reactions in crossed molecular beams: Vertical versus adiabatic H abstraction dynamics

Liu, Xianghong; Gross, Richard L.; Hall, Gregory E.; Muckerman, James T.; Suits, Arthur G.

doi:10.1063/1.1510444

Cited by 40 publications

(44 citation statements)

References 37 publications

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“…For the reaction of O( 3 P) + butane, Liu et al observed a similar trend and concluded that 4−5 kcal·mol −1 was not available for the product alkyl recoil. 63 Large polyatomic systems such as those studied here possess several repositories for the excess energies, in particular vibrations or rotations of the alkyl radical product. A simple hybrid Franck−Condon/impulsive model has been developed to account for the rotational excitation E rot of the alkyl radical product in the F + ethane reaction: 93…”

Section: Discussionmentioning

confidence: 99%

Dynamics of Chlorine Atom Reactions with Hydrocarbons: Insights from Imaging the Radical Product in Crossed Beams

et al. 2014

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We present a comprehensive overview of our ongoing studies applying dc slice imaging in crossed molecular beams to probe the dynamics of chlorine atom reactions with polyatomic hydrocarbons. Our approach consists in measuring the full velocity-flux contour maps of the radical products using vacuum ultraviolet "soft" photoionization at 157 nm. Our overall goal is to extend the range of chemical dynamics investigations from simple triatomic or tetraatomic molecules to systematic investigations of a sequence of isomers or a homologous series of reactants of intermediate size. These experimental investigations are augmented by high-level ab initio calculations which, taken together, reveal trends in product energy and angular momentum partitioning and offer deep insight into the reaction mechanisms as a function of structure, bonding patterns, and kinematics. We explore these issues in alkanes, for which only direct reactive encounters are found, and in unsaturated hydrocarbons, for which an addition-elimination mechanism competes with direct abstraction. The results for alkene addition-elimination in particular suggest a new view of these reactions: The only pathway to HCl elimination is accessed by means of roaming excursions of the Cl atom from the strongly bound adduct.

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Section: Discussionmentioning

confidence: 99%

Dynamics of Chlorine Atom Reactions with Hydrocarbons: Insights from Imaging the Radical Product in Crossed Beams

et al. 2014

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“…This work builds upon previous crossed-beamreactive-scattering studies of F + CH 4 /CD 4 by Liu, Harper, and others, [44][45][46] REMPI studies of Cl+ alkanes of Zare, OrrEwing, Kitsopolous, 38,39,47,48 as well as extensive studies of O͑ 3 P͒ + methane and nonmethane hydrocarbons by Suits, McKendrick, and others. 29,41,49,50 The work also builds on early FTIR studies of the F + C 2 H 6 system by Setser and co-workers, who report relative HF͑v =1,2,3͒ vibrational energy distributions, 51 although under incompletely "arrested" rotational relaxation conditions.…”

Section: Introductionmentioning

confidence: 96%

“…This has provided further incentive for atom + polyatom crossed beam studies with spectroscopic-based detection of products, as explored by Liu, Zare, Suits, Valentini, and others. [37][38][39][40][41] Counterbalancing these challenges, however, is the substantially richer world of reaction dynamics that opens up at the atom+ polyatom level. Consider, for example, a simple atom abstraction in a highly exothermic atom+ polyatom system.…”

Section: Introductionmentioning

confidence: 98%

Reactive scattering dynamics in atom+polyatomic systems: F+C2H6→HF(v,J)+C2H5

Whitney¹,

Zolot²,

McCoy³

et al. 2005

The Journal of Chemical Physics

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State-to-state scattering dynamics of F+C2H6-->HF(v,J)+C2H5 have been investigated at Ecom=3.2(6) kcalmol under single-collision conditions, via detection of nascent rovibrationally resolved HF(v,J) product states with high-resolution infrared laser absorption methods. State-resolved Doppler absorption profiles are recorded for multiple HF(v,J) transitions originating in the v=0,1,2,3 manifold, analyzed to yield absolute column-integrated densities via known HF transition moments, and converted into nascent probabilities via density-to-flux analysis. The spectral resolution of the probe laser also permits Doppler study of translational energy release into quantum-state-resolved HF fragments, which reveals a remarkable linear correlation between (i) HF(v,J) translational recoil and (ii) the remaining energy available, Eavail=Etot-E(HF(v,J)). The dynamics are interpreted in the context of a simple impulsive model based on conservation of linearangular momentum that yields predictions in good agreement with experiment. Deviations from the model indicate only minor excitation of ethyl vibrations, in contrast with a picture of extensive intramolecular vibrational energy flow but consistent with Franck-Condon excitation of the methylene CH2 bending mode. The results suggest a relatively simple dynamical picture for exothermic atom+polyatomic scattering, i.e., that of early barrier dynamics in atom+diatom systems but modified by impulsive recoil coupling at the transition state between translationalrotational degrees of freedom.

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“…The first method uses a calibration reaction for which the DCS is known from CMB experiments, 26,27 and the second is to use the outcomes of a comprehensive Monte-Carlo (MC) simulation of the experiments that is similar in spirit to the approach used by Suits and coworkers for a related experimental design. 80 In both cases an angular correction function is generated, and the two are similar in form and magnitude. The details of the first method have been described elsewhere, 32 but, in brief, an experimental angular correction function was obtained by comparison of dual molecular beam images for reaction (4) with CMB and VMI results reported by Huang et al 27 at a similar collision energy.…”

Section: Dual Beam Imagingmentioning

confidence: 99%

Velocity map imaging the dynamics of the reactions of Cl atoms with neopentane and tetramethylsilane

Rose

Greaves

Orr-Ewing

2010

The Journal of Chemical Physics

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Imaging O(3P)+alkane reactions in crossed molecular beams: Vertical versus adiabatic H abstraction dynamics

Abstract: Articles you may be interested inExploring the dynamics of reaction N + SiH 4 with crossed molecular-beam experiments and quantum-chemical calculations

Cited by 40 publications

References 37 publications

Dynamics of Chlorine Atom Reactions with Hydrocarbons: Insights from Imaging the Radical Product in Crossed Beams

Dynamics of Chlorine Atom Reactions with Hydrocarbons: Insights from Imaging the Radical Product in Crossed Beams

Reactive scattering dynamics in atom+polyatomic systems: F+C2H6→HF(v,J)+C2H5

Velocity map imaging the dynamics of the reactions of Cl atoms with neopentane and tetramethylsilane

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