Diabatization Schemes for Generating Charge-Localized Electron–Proton Vibronic States in Proton-Coupled Electron Transfer Systems

2011 ◽  
Vol 7 (9) ◽  
pp. 2831-2841 ◽  
Author(s):  
Andrew Sirjoosingh ◽  
Sharon Hammes-Schiffer
Keyword(s):  
Electron Transfer ◽  
Proton Coupled Electron Transfer ◽  
Vibronic States

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

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.

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

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.

scholarly journals Proton-coupled electron transfer reactions: analytical rate constants and case study of kinetic isotope effects in lipoxygenase

2016 ◽  
Vol 195 ◽  
pp. 171-189 ◽  
Author(s):  
Alexander V. Soudackov ◽  
Sharon Hammes-Schiffer
Keyword(s):  
Electron Transfer ◽  
Rate Constant ◽  
Isotope Effects ◽  
Thermal Fluctuations ◽  
Proton Donor ◽  
Nonadiabatic Transitions ◽  
Proton Coupled Electron Transfer ◽  
Wide Range ◽  
Donor Acceptor ◽  
Vibronic States

A general theory has been developed for proton-coupled electron transfer (PCET), which is vital to a wide range of chemical and biological processes. This theory describes PCET reactions in terms of nonadiabatic transitions between reactant and product electron–proton vibronic states and includes the effects of thermal fluctuations of the solvent or protein environment, as well as the proton donor–acceptor motion. Within the framework of this general PCET theory, a series of analytical rate constant expressions has been derived for PCET reactions in well-defined regimes. Herein, the application of this theory to PCET in the enzyme soybean lipoxygenase illustrates the regimes of validity for the various rate constant expressions and elucidates the fundamental physical principles dictating PCET reactions. Such theoretical studies provide significant physical insights that guide the interpretation of experimental data and lead to experimentally testable predictions. A combination of theoretical treatments with atomic-level simulations is essential to understanding PCET.

scholarly journals Electron–Nuclear Dynamics Accompanying Proton-Coupled Electron Transfer

2021 ◽  
Vol 143 (8) ◽  
pp. 3104-3112
Author(s):  
Yusuke Yoneda ◽  
S. Jimena Mora ◽  
James Shee ◽  
Brian L. Wadsworth ◽  
Eric A. Arsenault ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Nuclear Dynamics ◽  
Proton Coupled Electron Transfer

Facile proton-coupled electron transfer enabled by coordination-induced E–H bond weakening to boron

2021 ◽  
Author(s):  
Anthony Wong ◽  
Arunavo Chakraborty ◽  
Deependra Bawari ◽  
Guang Wu ◽  
Roman Dobrovetsky ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Proton Coupled Electron Transfer

Coordination induced bond weakening (CIBW) leads to facile PCET at various E–H bonds.

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