Transition state dynamics of the OH+H2O hydrogen exchange reaction studied by dissociative photodetachment of H3O2-

Deyerl, Hans-Jürgen; Luong, A. Khai; Clements, Todd G.; Continetti, Robert E.

doi:10.1039/a909619a

Cited by 38 publications

(36 citation statements)

References 23 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…2 As discussed below, these adiabatic curves are located around the transition state for the neutral bimolecular reaction, and they correlate with the different vibrational states of the OHϩOH products in the entrance or OϩH 2 O products in the exit channel. Examination of the E T distribution for each correlation band shows some variation, and may represent an important observable for comparison with future dynamics calculations.…”

mentioning

confidence: 93%

“…1 Photoelectron-photofragment coincidence ͑PPC͒ spectroscopy can extend these studies significantly by allowing characterization of the entire dissociative photodetachment ͑DPD͒ event. 2 DPD occurs when removal of an electron from a stable anion produces a neutral in a dissociative or metastable state that undergoes rapid dissociation. For stable negative ions in a nuclear configuration similar to that of the transition state of a bimolecular reaction, photodetachment can be used to access the transition state region.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Transition state dynamics of the OH+OH→O+H2O reaction studied by dissociative photodetachment of H2O2−

Deyerl

Clements

Luong

et al. 2001

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

Photoelectron-photofragment coincidence ͑PPC͒ spectroscopy has been used to study the dissociative photodetachment of H 2 O 2 Ϫ and D 2 O 2 Ϫ . The observed partitioning of photoelectron and photofragment translational energies provides information on the dynamics in the transition state region of the reaction between two hydroxyl radicals: OHϩOH→O( 3 P)ϩH 2 O. The data reveal vibrationally resolved product translational energy distributions for both the entrance channel OHϩOH and the exit channel O( 3 P)ϩH 2 O upon photodetachment. The total translational energy distribution shows a convoluted vibrational progression consistent with antisymmetric stretch excitation of H 2 O in the exit channel and OH stretch in the entrance channel. The photoelectron spectra are compared to two-dimensional time-dependent wave packet dynamics simulations based on an anharmonic potential in the anion and a model collinear potential energy surface for the neutral complex. The PPC spectra also yield the dissociation energies D 0 (H 2 O 2 Ϫ →H 2 OϩO Ϫ ) ϭ1.15Ϯ0.08 eV and D 0 (D 2 O 2 Ϫ →D 2 OϩO Ϫ )ϭ1.05Ϯ0.08 eV.

show abstract

mentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Transition state dynamics of the OH+OH→O+H2O reaction studied by dissociative photodetachment of H2O2−

Deyerl

Clements

Luong

et al. 2001

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

show abstract

“…In particular, the ability to form an unstable radical or reactive neutral molecule after electron ejection has enabled reaction intermediates, or fleeting transition states to be probed. [1][2][3] The ejection of an electron is assumed as sudden and the neutral formed is free to evolve in the absence of the electron. Given that a major remaining challenge for chemical physics is to develop experimental probes of how a chemical reaction system evolves when immersed in solution, it is yet to be seen whether photodetachment will provide a powerful way to initiate and study dynamics of such transients in a fully solvated environment.…”

Section: Introductionmentioning

confidence: 99%

The ejection distribution of solvated electrons generated by the one-photon photodetachment of aqueous I− and two-photon ionization of the solvent

Kloepfer

Vilchiz

Lenchenkov

et al. 2000

The Journal of Chemical Physics

194

362

View full text Add to dashboard Cite

Articles you may be interested inOne-photon photodetachment of I − in glycerol: Spectra and yield of solvated electrons in the temperature range 329 T 536 K Mechanisms of the ultrafast production and recombination of solvated electrons in weakly polar fluids: Comparison of multiphoton ionization and detachment via the charge-transfer-to-solvent transition of Na − in THF The spectra and the relative yield of solvated electrons produced by resonant photodetachment of iodide anion in ethylene glycol in the temperature range 296T453 K Two-photon dissociation and ionization of liquid water studied by femtosecond transient absorption spectroscopyThe ultrafast dynamics following one-photon UV photodetachment of I Ϫ ions in aqueous solution are compared with those following two-photon ionization of the solvent. Ultrafast pump-probe experiments employing 50 fs ultraviolet pulses reveal similar and very rapid time scales for electron ejection. However, the electron ejection process from water pumped into the conduction band and from iodide ions detached at threshold are readily distinguishable. The observed picosecond timescale geminate recombination and electron escape dynamics are reconstructed using two different models, a diffusion-limited return of the electron from ϳ15 Å to its parent and a competing kinetics model governed by the reverse electron transfer rate. We conclude that the ''ejected'' electron in the halide detachment is merely separated from the halogen atom within the same solvent shell. The assignment of detachment into a contact pair is based on the recombination profile rather than by the postulate of any new spectral absorption due to an electron in a contact pair. The contact pair is surprisingly long-lived and the nonadiabatic recombination is rather slow considering the proximity of the partners. Experiments in mixed solvents confirm our assignment of the two distinct ejection mechanisms. The detachment mechanism is therefore fundamentally different in the resonant ͑one photon͒ charge-transfer-to-solvent ͑CTTS͒ process from the multiphoton detachment of aqueous iodide ions, which bears more similarity to the direct solvent ionization.

show abstract

“…Schaefer et al4, 5 have carried out extensive ab initio investigations on the complex formation between the OH radical and a water molecule. In addition, several research groups have carried out ab initio investigations on reaction 1 3, 6–14. In the present work, we have focused our attention upon the structures and the association energy of the entrance complex and also upon the reaction path for hydrogen atom abstraction reaction 1.…”

Section: Introductionmentioning

confidence: 99%

Ab initioinvestigation on the reaction path and rate for the gas‐phase reaction of HO + H₂O ↔ H₂O + OH

et al. 2003

View full text Add to dashboard Cite

This article describes an ab initio investigation on the potential surfaces for one of the simplest hydrogen atom abstraction reactions, that is, HO + H2O <--> H2O + OH. In accord with the findings in the previously reported theoretical investigations, two types of the hydrogen-bonding complexes [HOH--OH] and [H2O--HO] were located on the potential energy surface. The water molecule acts as a hydrogen donor in the [HOH--OH] complex, while the OH radical acts as a hydrogen donor in the [H2O--HO] complex. The energy evaluations at the MP2(FC) basis set limit, as well as those through the CBS-APNO procedure, have provided estimates for enthalpies of association for these complexes at 298 K as -2.1 approximately -2.3 and -4.1 approximately -4.3 kcal/mol, respectively. The IRC calculations have suggested that the [H2O--HO] complex should be located along the reaction coordinate for the hydrogen abstraction. Our best estimate for the classical barrier height for the hydrogen abstraction is 7.8 kcal/mol, which was obtained from the CBS-APNO energy evaluations. After fitting the CBS-APNO potential energy curve to a symmetrical Eckart function, the rate constants were calculated by using the transition state theory including the tunneling correction. Our estimates for the Arrhenius parameters in the temperature region from 300 to 420 K show quite reasonable agreement with the experimentally derived values.

show abstract

Transition state dynamics of the OH+H2O hydrogen exchange reaction studied by dissociative photodetachment of H3O2-

Cited by 38 publications

References 23 publications

Transition state dynamics of the OH+OH→O+H2O reaction studied by dissociative photodetachment of H2O2−

Transition state dynamics of the OH+OH→O+H2O reaction studied by dissociative photodetachment of H2O2−

The ejection distribution of solvated electrons generated by the one-photon photodetachment of aqueous I− and two-photon ionization of the solvent

Ab initioinvestigation on the reaction path and rate for the gas‐phase reaction of HO + H₂O ↔ H₂O + OH

Contact Info

Product

Resources

About

Transition state dynamics of the OH+H2O hydrogen exchange reaction studied by dissociative photodetachment of H3O2-

Cited by 38 publications

References 23 publications

Transition state dynamics of the OH+OH→O+H2O reaction studied by dissociative photodetachment of H2O2−

Transition state dynamics of the OH+OH→O+H2O reaction studied by dissociative photodetachment of H2O2−

The ejection distribution of solvated electrons generated by the one-photon photodetachment of aqueous I− and two-photon ionization of the solvent

Ab initioinvestigation on the reaction path and rate for the gas‐phase reaction of HO + H2O ↔ H2O + OH

Contact Info

Product

Resources

About

Ab initioinvestigation on the reaction path and rate for the gas‐phase reaction of HO + H₂O ↔ H₂O + OH