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Transition state spectroscopy of open shell systems: Angle-resolved photodetachment spectra for the adiabatic singlet states of OHF

AuthorsGómez Carrasco, Susana ; Aguado, Alfredo ; Paniagua, Miguel; Roncero, Octavio
KeywordsTransition state spectroscopy
Ab initio
Potential energy surface
Conical intersections
Reaction dynamics
Issue Date2-Feb-2007
CitationJournal of Photochemistry and Photobiology A: Chemistry 190(2-3): 145-160 (2007)
AbstractIn this work three-dimensional potential energy surfaces of the first five singlet states of OHF are developed based on fits of more than 10,000 highly accurate ab initio points. An approximate treatment is presented for the calculation of the anisotropy parameter describing the electron angular distribution photodetached from a molecular anion. This method is used to calculate the angle-resolved photoelectron spectra in the photodetachment of OHF−. The wave packet formed in the neutral OHF system is placed at the transition state region, and yields the formation of OH + F and HF + O products. The results are compared with the recent experimental measurements published by Neumark [D.M. Neumark, Phys. Chem. Chem. Phys. 7 (2005) 433]. The intensity found at low electron kinetic energy including these five states and the three lower triplet states is found to be low. To analyze the effect of higher electronic states more excited 1Σ−, 3Σ+ and 3Δ states are calculated at collinear geometry. The agreement with the experimental data improves, thus demonstrating that the correct simulation of the photodetachment spectrum at 213 nm involves at least 12 electronic states. All the structures of the experimental spectra are semiquantitatively reproduced finding an overall good agreement. It is concluded that the main problem of the simulation is in the intensity and anisotropy parameters. An alternative to their calculation would be to fit their values to reproduce the experimental results, but this would require to separate the contribution arising from different final electronic states.
Description16 pages, 13 figures, 2 tables.-- Printed version published Aug 15, 2007.-- Issue title: "Theoretical Aspects of Photoinduced Processes in Complex Systems".
Publisher version (URL)http://dx.doi.org/10.1016/j.jphotochem.2007.01.027
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