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:

^[1]; 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

Sponsoring Org.:: USDOE

OSTI Identifier:: 1226187

Grant/Contract Number:: Center for Molecular Electrocatalysis

Resource 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

Country of Publication:: United States

Language:: English

Citation Formats


                    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., 2015. 
        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. Tue .  
        "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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DOI: 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

Journal Article Soudackov, Alexander ; Hammes-Schiffer, Sharon - Journal of Chemical Physics

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 regimes for the proton donor-acceptor vibrational mode. 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 does not significantly impact the rate constants derived using the cumulant expansion approachmore »« less
DOI: 10.1063/1.4935045
Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

Journal Article Soudackov, Alexander V. ; Hammes-Schiffer, Sharon - Journal of Chemical Physics

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
DOI: 10.1063/1.4935045
Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

Journal Article Soudackov, Alexander V. ; Hammes-Schiffer, Sharon - Journal of Chemical Physics

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
DOI: 10.1063/1.4935045
Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

Journal Article Soudackov, Alexander V. ; Hammes-Schiffer, Sharon - Journal of Chemical Physics
DOI: 10.1063/1.4935045
Quantum and dynamical effects of proton donor-acceptor vibrational motion in nonadiabatic proton-coupled electron transfer reactions

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This paper presents a general theoretical formulation for proton-coupled electron transfer (PCET) reactions. The solute is represented by a multistate valence bond model, and the active electrons and transferring proton(s) are treated quantum mechanically. This formulation enables the classical or quantum mechanical treatment of the proton donor-acceptor vibrational mode, as well as the dynamical treatment of the proton donor-acceptor mode and the solvent. Nonadiabatic rate expressions are presented for PCET reactions in a number of well-defined limits for both dielectric continuum and molecular representations of the environment. The dynamical rate expressions account for correlations between the fluctuations of the protonmore »« less
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