Ions Can Move a Proton-Coupled Electron-Transfer Reaction into Tunneling Regime

The calculations unravel the role of buffers in the kinetics of the proton-coupled electron transfer reaction between α-hydroxyethyl radical and bromoacetate.

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Quasi Diabatic Propagation Scheme for Direct Simulation of Proton-Coupled Electron Transfer Reaction

10.26434/chemrxiv.7545032.v1 ◽

2019 ◽

Author(s):

Farnaz A. Shakib ◽

Pengfei Huo

Keyword(s):

Electron Transfer ◽

Transfer Reaction ◽

A Priori ◽

Electron Transfer Reaction ◽

Integral Approach ◽

Direct Simulation ◽

Diabatic States ◽

Proton Coupled Electron Transfer ◽

Correct Reaction ◽

Vibronic States

We apply a recently-developed quasi-diabatic (QD) propagation scheme to simulate proton-coupled electron transfer (PCET) reactions. This scheme enables a direct interface between an accurate diabatic dynamics approach and the adiabatic vibronic states. It explicitly avoids theoretical efforts to pre-construct diabatic states for the transferring electron and proton or reformulate diabatic dynamics methods to the adiabatic representation, both of which are non-trivial tasks. Using partial linearized path-integral approach and symmetrical quasi-classical approach as the diabatic dynamics methods, we demonstrate that the QD propagation scheme provides accurate vibronic dynamics of PCET reactions and reliably predict the correct reaction mechanism without any a priori assumptions. This work demonstrates the possibility to directly simulate challenging PCET reactions by using accurate diabatic dynamics approaches and adiabatic vibronic information.

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Quasi Diabatic Propagation Scheme for Direct Simulation of Proton-Coupled Electron Transfer Reaction

10.26434/chemrxiv.7545032 ◽

2019 ◽

Author(s):

Farnaz A. Shakib ◽

Pengfei Huo

Keyword(s):

Electron Transfer ◽

Transfer Reaction ◽

A Priori ◽

Electron Transfer Reaction ◽

Integral Approach ◽

Direct Simulation ◽

Diabatic States ◽

Proton Coupled Electron Transfer ◽

Correct Reaction ◽

Vibronic States

We apply a recently-developed quasi-diabatic (QD) propagation scheme to simulate proton-coupled electron transfer (PCET) reactions. This scheme enables a direct interface between an accurate diabatic dynamics approach and the adiabatic vibronic states. It explicitly avoids theoretical efforts to pre-construct diabatic states for the transferring electron and proton or reformulate diabatic dynamics methods to the adiabatic representation, both of which are non-trivial tasks. Using partial linearized path-integral approach and symmetrical quasi-classical approach as the diabatic dynamics methods, we demonstrate that the QD propagation scheme provides accurate vibronic dynamics of PCET reactions and reliably predict the correct reaction mechanism without any a priori assumptions. This work demonstrates the possibility to directly simulate challenging PCET reactions by using accurate diabatic dynamics approaches and adiabatic vibronic information.

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Polymer stabilized silver nanoparticle: An efficient catalyst for proton-coupled electron transfer reaction and the electrochemical recognition of biomolecule

Chemical Physics Letters ◽

10.1016/j.cplett.2014.05.101 ◽

2014 ◽

Vol 608 ◽

pp. 145-151 ◽

Cited By ~ 15

Author(s):

Meenakshi Choudhary ◽

Samarjeet Siwal ◽

Rafique Ul Islam ◽

Michael J. Witcomb ◽

Kaushik Mallick

Keyword(s):

Electron Transfer ◽

Silver Nanoparticle ◽

Transfer Reaction ◽

Electron Transfer Reaction ◽

Efficient Catalyst ◽

Proton Coupled Electron Transfer ◽

Electrochemical Recognition ◽

Polymer Stabilized

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