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  • 2000-2004  (2)
  • 1
    Electronic Resource
    Electronic Resource
    The low-temperature reactive tunneling in condensed phase. II. Multidimensional transition model (2001)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 115 (2001), S. 6083-6094 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The dynamical model of tunneling interlevel transitions is extended to describe the kinetics of H-atom transfer in real reactions proceeding in the condensed phase. The reaction mechanism includes an explicit consideration of three modes; the high-frequency reactive motion of the H atom, the low-frequency intermolecular promotion mode, and an intramolecular mode which changes significantly during the reaction and is associated with the hybridization geometry changes of the reaction center. The rate constant expression is derived in terms of the standard technique of the theory of radiationless transitions. Its high- and moderate-temperature analysis reproduces the results obtained earlier in the framework of the Golden Rule approach. Peculiarities of the present theory are revealed beyond this temperature range. A remarkable low-temperature threshold effect causes steep temperature trends in the reaction rate which are likely to account for some recent kinetic experiments. © 2001 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.1397355
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  • 2
    Electronic Resource
    Electronic Resource
    The low temperature reactive tunneling in condensed phase. I. The rate expression (2001)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 115 (2001), S. 6072-6082 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We study how the quantization of energy levels affects the deep tunneling rate expression for a double-well system immersed in a harmonic bath. The model of tunneling transitions implies that the energy of a tunneling system is not conserved during a transition because its interaction with the environment is explicitly taken into account. The Golden Rule approach invoked usually cannot be directly applied for such a model. We consider its modification in which the expression for the rate constant depends symmetrically on spectral line shapes of energy levels in both reactant and product wells. The derivation is based on the Breit–Wigner resonance expansion of a dynamical transition probability which is extended on condensed phase systems and averaged at the next stage over fluctuations of the energy levels promoted by system/environment interactions. Test computations for a one-dimensional model case demonstrate novel features inherent to this approach which are clearly revealed in the low-temperature kinetic regime. © 2001 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.1397335
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
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