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Quantum and Non-Markovian Effects in the Electron Transfer Reaction Dynamics in the Marcus Inverted Region

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Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Phys. Chem. 1996, 100, 8, 3056-3062
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    Quantum and Non-Markovian Effects in the Electron Transfer Reaction Dynamics in the Marcus Inverted Region
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    Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore-560012, India
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    The Journal of Physical Chemistry

    Cite this: J. Phys. Chem. 1996, 100, 8, 3056–3062
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    https://doi.org/10.1021/jp9525550
    Published February 22, 1996
    Copyright © 1996 American Chemical Society
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    Abstract

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    Electron transfer reactions in large molecules may often be coupled to both the polar solvent modes and the intramolecular vibrational modes of the molecule. This can give rise to a complex dynamics which may in some systems, like betaine, be controlled more by vibrational rather than by solvent effects. Additionally, a significant contribution from an ultrafast relaxation component in the solvation dynamics may enhance the complexity. To explain the wide range of behavior that has been observed experimentally, Barbara et al. recently proposed that a model of an electron transfer reaction should minimally consist of a low-frequency classical solvent mode (X), a low-frequency vibrational mode (Q), and a high-frequency quantum mode (q) (J. Phys. Chem. 1991, 96, 3728). In the present work, a theoretical study of this model is described. This study generalizes earlier work by including the biphasic solvent response and the dynamics of the low-frequency vibrational mode in the presence of a delocalized, extended reaction zone. A novel Green's function technique has been developed which allowed us to study the non-Markovian dynamics on a multidimensional surface. The contributions from the high-frequency vibrational mode and the ultrafast component in the non-Markovian solvent dynamics are found to be primarily responsible for the dramatic increase in charge transfer rate over the prediction of the classical theories that neglect both these factors. These, along with a large coupling between the reactant and the product states, may combine to render the electron transfer rate both very large and constant over a wide range of solvent relaxation rates. A study on the free energy gap dependence of the electron transfer rate reveals that the rates are sensitive to changes in the quantum frequency particularly when the free energy gap is very large.

    Copyright © 1996 American Chemical Society

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     Author to whom correspondence should be addressed. E-mail:  [email protected].

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     Abstract published in Advance ACS Abstracts, January 15, 1996.

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    15. N. Gayathri and, B. Bagchi. Free Energy Gap Dependence of the Electron-Transfer Rate from the Inverted to the Normal Region. The Journal of Physical Chemistry A 1999, 103 (42) , 8496-8504. https://doi.org/10.1021/jp991357w
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    42. Biman Bagchi, N. Gayathri. Interplay Between Ultrafast Polar Solvation and Vibrational Dynamics in Electron Transfer Reactions: Role of High‐Frequency Vibrational Modes. 1999, 1-80. https://doi.org/10.1002/9780470141663.ch1
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    46. N. Gayathri, S. Bhattacharyya, B. Bagchi. Dynamic solvent effects on the vibrational overtone dephasing in molecular liquids: Subquadratic quantum number dependence. The Journal of Chemical Physics 1997, 107 (24) , 10381-10390. https://doi.org/10.1063/1.474201
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    Cite this: J. Phys. Chem. 1996, 100, 8, 3056–3062
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jp9525550
    Published February 22, 1996
    Copyright © 1996 American Chemical Society
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