Transition state dynamics of the OH ¿ OH \ O ¿ H 2 O reaction studied by dissociative photodetachment of H
نویسندگان
چکیده
Photoelectron-photofragment coincidence ~PPC! spectroscopy has been used to study the dissociative photodetachment of H2O2 2 and D2O2 . 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: OH1OH→O(P)1H2O. The data reveal vibrationally resolved product translational energy distributions for both the entrance channel OH1OH and the exit channel O(P)1H2O upon photodetachment. The total translational energy distribution shows a convoluted vibrational progression consistent with antisymmetric stretch excitation of H2O 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 D0(H2O2 →H2O1O) 51.1560.08 eV and D0(D2O2 →D2O1O)51.0560.08 eV. © 2001 American Institute of Physics. @DOI: 10.1063/1.1404148#
منابع مشابه
Probing the transition state via photoelectron and photodetachment spectroscopy of H(3)O(-).
The H(3)O(-) anion has stable and metastable structures that resemble configurations in the vicinity of the transition state for the neutral reactions OH + H(2) <--> H(2)O + H. Photoelectron spectroscopy of this anion probes the neutral reaction dynamics in the critical transition-state region. Accurate quantum dynamics calculations of the photoelectron intensity and photodissociation product e...
متن کاملTransition State Spectroscopy of the OH + H 2 - H 20 + H Reaction Via Photodetachment of H 3 O - and D 30 -
The transition state region of the reaction OH + H2 -. H2O + H is investigated by photoelectron spectroscopy of the H3Oand D30anions. The peaks observed in the spectra are from a combination of vibrational progressions and overlapping anion -. neutral electronic transitions. The photoelectron angular distributions indicate that two processes contribute to the spectra; these are assigned to phot...
متن کاملDynamics on the HOCO potential energy surface studied by dissociative photodetachment of HOCO- and DOCO-.
An experimental study of the dissociative photodetachment (DPD) dynamics of HOCO(-) and DOCO(-) at a photon energy of 3.21 eV has been carried out to probe the potential energy surface of the HOCO free radical and the dynamics of the OH+CO-->H+CO(2) reaction. These photoelectron-photofragment coincidence experiments allow the identification of photodetachment processes leading to the production...
متن کاملInitial state-selected reaction probabilities for OH+H,-+H+H,O and photodetachment intensities for HOH;
We have used a discrete variable representation (DVR) with absorbing boundary conditions (ABC) to calculate initial state-selected reaction probabilities and photodetachment intensities. We apply this method to the OH + H, reaction constrained to a plane with the OH bond frozen. The calculated reaction probabihties have al1 the qualitative features observed in full dimensional calculations. We ...
متن کاملReaction Dynamics of NH2+OH on an Interpolated Potential Energy Surface
QCT calculations were performed to study the behavior of energized NH2OH formed by association collision of NH2 radical with OH radical. A potential energy surface that describes the behavior of the title reaction has been constructed by interpolation of ab initio data. H2O, HON, HNO, NH3, O, H2NO, cis or trans-HONH, and H products and two vibrationally energized NH2OH and NH3O adducts were obs...
متن کامل