Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

doi:10.1063/1.4935045

Title: Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

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Authors:

; Hammes-Schiffer, Sharon ^[1]

Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Ave., Urbana, Illinois 61801, USA

Publication Date:: 2015-11-17

Grant/Contract Number:: Center for Molecular Electrocatalysis

Type:: Publisher's Accepted Manuscript

Journal Name:: The Journal of Chemical Physics

Additional Journal Information:: Journal Name: The Journal of Chemical Physics Journal Volume: 143 Journal Issue: 19; Journal ID: ISSN 0021-9606

Publisher:: American Institute of Physics

Sponsoring Org:: USDOE

Country of Publication:: United States

Language:: English

OSTI Identifier:: 1226187


                    Soudackov, Alexander V., and Hammes-Schiffer, Sharon. Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion.  United States: N. p.,  
        Web.  doi:10.1063/1.4935045.

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                    Soudackov, Alexander V., & Hammes-Schiffer, Sharon. Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion.  United States.  doi:10.1063/1.4935045.

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                    Soudackov, Alexander V., and Hammes-Schiffer, Sharon. 2015.  
        "Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion".  United States.  
        doi:10.1063/1.4935045.

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@article{osti_1226187,

  title        = {Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion},

  author       = {Soudackov, Alexander V. and Hammes-Schiffer, Sharon},

  abstractNote = {},

  doi          = {10.1063/1.4935045},

  journal      = {The Journal of Chemical Physics},

  number       = 19,

  volume       = 143,

  place        = {United States},

  year         = {2015},

  month        = {11}

}

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10.1063/1.4935045
https://doi.org/10.1063/1.4935045

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Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

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Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency proton donor-acceptor vibrational modes. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term in the framework of the cumulant expansion framework may significantly impact the rate constants at highmore »« less
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Title: Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

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