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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 110 (1999), S. 11117-11120 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The hydrogen atom products of the OH A 2Σ+ (v=0)+H2→H+H2O quenching reaction have been characterized by Doppler spectroscopy. The translational energy distribution of the products is bimodal, with the two components accounting for approximately 3% and 40% of the 4.72 eV of available energy. © 1999 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 110 (1999), S. 6732-6742 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The fundamental H2 vibration of the ortho-H2–OH complex in its ground electronic state has been observed at 4151.49±0.03 cm−1 via stimulated Raman excitation. The stimulated Raman transition has been identified with an ultraviolet probe laser using two different detection schemes. The transition was detected as a depletion in the H2–OH laser-induced fluorescence signal in the OH A 2Σ+–X 2Π (1,0) spectral region and through the appearance of OH A 2Σ+–X 2Π (0,1) laser-induced fluorescence following vibrational predissociation of the complex. Vibrational predissociation is found to proceed via a near-resonant pathway that transfers one quantum of vibrational excitation from H2 to OH. The remaining ∼529 cm−1 of available energy is distributed over excited rotational states of OH (v=1) and the lowest rotational level of ortho-H2 (v=1), with the balance flowing into translational recoil. The lifetime of vibrationally activated ortho-H2–OH (νH2=1) is determined to be less than 7 ns, the temporal resolution of the lasers, by monitoring the time evolution of the OH products. The results are compared with previous infrared studies of OH vibrational activation in ortho-H2–OH as well as full collision studies of the reaction of vibrationally excited H2 with OH. © 1999 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 109 (1998), S. 10707-10718 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: State-selective infrared excitation of o-H2–OH via the pure OH overtone transition has been used to induce a half-collision inelastic scattering event between the OH radical and ortho-H2 under restricted initial orientation conditions. The time evolution and final state distribution of the OH products from vibrational predissociation have been evaluated by ultraviolet probe laser-induced fluorescence measurements. The half-collision scattering takes place with ∼3350 cm−1 of energy available to the OH (v=1)+o-H2 products, an energy that exceeds the classical barrier to reaction. The OH (v=1) products are preferentially populated in high rotational levels with a distribution that is consistent with an energy gap law. A significant fraction of the OH fragments are promoted to the excited spin–orbit state in the predissociation process. A strong lambda-doublet propensity is also found, indicating that the OH unpaired pπ orbital is preferentially aligned perpendicular to the rotational plane of the OH products. Finally, the OH rotational and fine structure distributions are compared with those obtained in previous full collision inelastic scattering studies at energies below the threshold for reaction. © 1998 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 109 (1998), S. 3461-3473 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The rotationally resolved infrared spectrum of the prereactive o-H2–OH complex in its ground electronic state is obtained in the OH overtone region at ∼1.4 μm using an IR-UV double resonance fluorescence enhancement technique. The pure OH overtone band of o-H2–OH is observed as well as approximately 20 additional rovibrational transitions extending out to the OH (X 2Π,v=2)+o-H2(X 1Σg+) dissociation limit. These transitions are assigned as combination bands involving the simultaneous excitation of the OH vibrational overtone and intermolecular bending (internal rotor) states. The assignment of the experimental spectrum is aided by a detailed comparison with the bound states computed for the ab initio potential of Clary, Werner, and co-workers [Mol. Phys. 83, 405 (1994)]. The infrared spectroscopy results also verify the topology of this ab initio potential in the entrance channel to the OH+H2 hydrogen abstraction reaction. Direct time-resolved experiments indicate that the lifetime of the vibrationally activated o-H2–OH complex in the ground intermolecular state is 115(26) ns. The initial excitation is found to stay localized in the OH intramolecular stretching mode for a long period of time prior to vibrational predissociation or chemical reaction. © 1998 American Institute of Physics.
    Type of Medium: Electronic Resource
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