相关论文: Ring-polymer instanton theory of electron transfer…
Semiclassical instanton theory captures nuclear quantum effects such as tunnelling in chemical reactions. It was originally derived from two different starting points, the flux correlation function and the ImF premise. In pursuit of a…
Constructing an accurate approximation to nonadiabatic rate theory which is valid for arbitrary values of the electronic coupling has been a long-standing challenge in theoretical chemistry. Ring-polymer instanton theories offer a very…
Fermi's golden rule describes the leading-order behaviour of the reaction rate as a function of the diabatic coupling. Its asymptotic $(\hbar \rightarrow 0)$ limit is the semiclassical golden-rule instanton rate theory, which rigorously…
We propose a new quantum transition-state theory for calculating Fermi's golden-rule rates in complex multidimensional systems. This method is able to account for the nuclear quantum effects of delocalization, zero-point energy and…
Many reactions in chemistry and biology involve multiple electronic states, rendering them nonadiabatic in nature. These reactions can be formally described using Fermi's golden rule (FGR) in the weak-coupling limit. Nonadiabatic instanton…
We describe a path-integral molecular dynamics implementation of our recently developed golden-rule quantum transition-state theory (GR-QTST). The method is applied to compute the reaction rate in various models of electron transfer and…
We analyse the golden rule limit of the recently proposed isomorphic ring polymer (iso-RP) method. This method aims to combine an exact expression for the quantum mechanical partition function of a system with multiple electronic states…
We apply the newly derived nonadiabatic golden-rule instanton theory to asymmetric models describing electron-transfer in solution. The models go beyond the usual spin-boson description and have anharmonic free-energy surfaces with…
We present a general quantum instanton approach to calculating reaction rates for systems with two electronic states and arbitrary values of the electronic coupling. This new approach, which we call the non-adiabatic quantum instanton…
Ring-polymer instanton theory has been developed to simulate the quantum dynamics of molecular systems at low temperatures. Chemical reaction rates can be obtained by locating the dominant tunneling pathway and analyzing fluctuations around…
We present a simple interpolation formula for the rate of an electron transfer reaction as a function of the electronic coupling strength. The formula only requires the calculation of Fermi Golden Rule and Born-Oppenheimer rates and so can…
Fermi's golden rule defines the transition rate between weakly coupled states and can thus be used to describe a multitude of molecular processes including electron-transfer reactions and light-matter interaction. However, it can only be…
The Wolynes theory of electronically nonadiabatic reaction rates [P. G. Wolynes, J. Chem. Phys. 87, 6559 (1987)] is based on a saddle point approximation to the time integral of a reactive flux autocorrelation function in the nonadiabatic…
We present a simple method for the calculation of reaction rates in the Fermi golden-rule limit, which accurately captures the effects of tunnelling and zero-point energy. The method is based on a modification of the recently proposed…
We present a state-space-based path integral method to calculate the rate of electron transfer (ET) in multi-state, multi-electron condensed-phase processes. We employ an exact path integral in discrete electronic states and continuous…
We present a real-time path integral theory for the rate of electron transfer reactions. Using graph theoretic techniques, the dynamics is expressed in a formally exact way as a set of integral equations. With a simple approximation for the…
In this paper, we derive a perturbatively-corrected instanton rate theory in the ring-polymer framework (RPI+PC), which significantly enhances the accuracy of instanton theory by using third and fourth derivatives of the potential to…
We use a numerically exact real-time path integral Monte Carlo scheme to compute electron transfer dynamics between two redox sites within a spin-boson approach. The case of asymmetric reactions is studied in detail in the least understood…
We explore the relation between the quantum and semiclassical instanton approximations for the reaction rate constant. From the quantum instanton expression, we analyze the contributions to the rate constant in terms of minimum-action paths…
Instanton theory relates the rate constant for tunneling through a barrier to the periodic classical trajectory on the upturned potential energy surface whose period is $\tau=\hbar/(k_{\rm B}T)$. Unfortunately, the standard theory is only…