Bimolecular reaction rates from ring polymer molecular dynamics

2009 ◽  
Vol 130 (17) ◽  
pp. 174713 ◽  
Author(s):  
Rosana Collepardo-Guevara ◽  
Yury V. Suleimanov ◽  
David E. Manolopoulos
Keyword(s):  
Molecular Dynamics ◽  
Reaction Rates ◽  
Bimolecular Reaction ◽  
Ring Polymer ◽  
Ring Polymer Molecular Dynamics

Bimolecular reaction rates from ring polymer molecular dynamics: Application to H + CH4→ H2 + CH3

2011 ◽  
Vol 134 (4) ◽  
pp. 044131 ◽  
Author(s):  
Yury V. Suleimanov ◽  
Rosana Collepardo-Guevara ◽  
David E. Manolopoulos
Keyword(s):  
Molecular Dynamics ◽  
Reaction Rates ◽  
Bimolecular Reaction ◽  
Ring Polymer ◽  
Ring Polymer Molecular Dynamics

Mean field ring polymer molecular dynamics for electronically nonadiabatic reaction rates

2016 ◽  
Vol 195 ◽  
pp. 253-268 ◽  
Author(s):  
Jessica Ryan Duke ◽  
Nandini Ananth
Keyword(s):  
Molecular Dynamics ◽  
Mean Field ◽  
Golden Rule ◽  
Reaction Rates ◽  
State Theory ◽  
Time Dynamics ◽  
Ring Polymer ◽  
Ring Polymer Molecular Dynamics ◽  
Dividing Surface ◽  
Dynamics Simulations

We present a mean field ring polymer molecular dynamics method to calculate the rate of electron transfer (ET) in multi-state, multi-electron condensed-phase processes. Our approach involves calculating a transition state theory (TST) estimate to the rate using an exact path integral in discrete electronic states and continuous Cartesian nuclear coordinates. A dynamic recrossing correction to the TST rate is then obtained from real-time dynamics simulations using mean field ring polymer molecular dynamics. We employ two different reaction coordinates in our simulations and show that, despite the use of mean field dynamics, the use of an accurate dividing surface to compute TST rates allows us to achieve remarkable agreement with Fermi's golden rule rates for nonadiabatic ET in the normal regime of Marcus theory. Further, we show that using a reaction coordinate based on electronic state populations allows us to capture the turnover in rates for ET in the Marcus inverted regime.

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