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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 115 (2001), S. 5345-5348 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The dissociative photodetachment (DPD) of HCO2− and DCO2− was studied at 258 nm. State-resolved translational energy distributions were observed correlated to bending excitation in the CO2 product for the channel producing H/D+CO2, indicating very low rotational excitation in the products consistent with predissociation of a C2ν HCO2 molecule. No evidence was found for dissociation into OH+CO. All three low-lying electronic states (2A1, 2B2, and 2A2) were found to dissociate, but resolved progressions were only observed from photodetachment to the 2A1 and 2B2 states. Photoelectron-photofragment coincidence spectra for DCO2− show resolved vertical bands and indicate that multiple CO2 vibrational states are accessible from each vibrational level in the predissociating DCO2 molecule. The resolved structure is assigned to vibrational predissociation sequence bands, observable in this DPD process owing to the dissociation dynamics and the near degeneracy of the vibrational levels in the 2A1 and 2B2 states of HCO2 and the bending mode of the CO2 products. © 2001 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 114 (2001), S. 8436-8444 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Photoelectron–photofragment coincidence spectroscopy was used to study dissociative photodetachment of the doubly hydrated clusters of oxide and hydroxide, M−(H2O)2→M+2H2O+e− (M=O, OH). These experiments yield information on the energetics of the parent anion and the dissociation dynamics of the photodetached neutral species. Photoelectron spectra and photoelectron–photofragment coincidence spectra are presented and compared to data for O−(H2O) and OH−(H2O). Unlike the singly hydrated species, no evidence of vibrationally resolved product translational energy distributions is observed. The second hydration energy of O− with both H2O and D2O was also measured to be 0.80±0.08 and 0.81±0.08 eV, respectively. The three-body dissociation dynamics of the neutral clusters produced by photodetachment were studied by measuring the velocities and recoil angles of all the particles in coincidence. The observed partitioning of momentum is consistent with a two-step mechanism or dissociation from a wide range of starting geometries. © 2001 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 115 (2001), S. 6931-6940 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Photoelectron-photofragment coincidence (PPC) spectroscopy has been used to study the dissociative photodetachment of H2O2− 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: OH+OH→O(3P)+H2O. The data reveal vibrationally resolved product translational energy distributions for both the entrance channel OH+OH and the exit channel O(3P)+H2O 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−→H2O+O−)=1.15±0.08 eV and D0(D2O2−→D2O+O−)=1.05±0.08 eV. © 2001 American Institute of Physics.
    Type of Medium: Electronic Resource
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