Study of proton-coupled electron transfer (PCET) with four explicit diabatic states at the ab initio level

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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Proton-Coupled Electron Transfer versus Hydrogen Atom Transfer: Generation of Charge-Localized Diabatic States

The Journal of Physical Chemistry A ◽

10.1021/jp111210c ◽

2011 ◽

Vol 115 (11) ◽

pp. 2367-2377 ◽

Cited By ~ 117

Author(s):

Andrew Sirjoosingh ◽

Sharon Hammes-Schiffer

Keyword(s):

Electron Transfer ◽

Hydrogen Atom ◽

Hydrogen Atom Transfer ◽

Atom Transfer ◽

Diabatic States ◽

Proton Coupled Electron Transfer

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Introducing a closed system approach for the investigation of chemical steps involving proton and electron transfer; as illustrated by a copper-based water oxidation catalyst

Physical Chemistry Chemical Physics ◽

10.1039/c6cp07454e ◽

2017 ◽

Vol 19 (6) ◽

pp. 4208-4215 ◽

Cited By ~ 5

Author(s):

Jessica M. de Ruiter ◽

Francesco Buda

Keyword(s):

Molecular Dynamics ◽

Electron Transfer ◽

Reaction Mechanism ◽

Ab Initio ◽

Closed System ◽

Water Oxidation ◽

System Approach ◽

Oxidation Catalyst ◽

Proton Coupled Electron Transfer

We present an ab initio molecular dynamics approach to characterize proton-coupled electron transfer catalytic steps and identify the preferred reaction mechanism.

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