Related papers: Nonadiabatic quantum transition-state theory in th…
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…
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…
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…
Electron transfer reactions play an essential role in many chemical and biological processes. Fermi's Golden rule, which assumes that the coupling between electronic states is small, has formed the foundation of electron transfer rate…
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…
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…
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…
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…
We take the golden-rule instanton method derived in the previous paper [arXiv:1509.04919] and reformulate it using a ring-polymer approach. This gives equations which can be used to compute the rates of electron-transfer reactions in the…
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…
A novel and readily understandable derivation of the Golden Rule of time dependent perturbation theory is presented. The derivation is based on adiabatic turning on of the perturbation as used, for instance, in some formal developments of…
Starting from a general molecular Hamiltonian expressed in the basis of adiabatic electronic and nuclear position states, where a compact and complete expression for nonadiabatic derivative coupling (NDC) Hamiltonian term is obtained, we…
We review the calculation of Fermi's golden rule for a system of $N$-body dipoles, magnetic or electric, weakly interacting with a blackbody radiation. By using the magnetic or electric field-field correlation function evaluated in the…
We present a Gedankenexperiment that leads to a violation of detailed balance if quantum mechanical transition probabilities are treated in the usual way by applying Fermi's "golden rule". This Gedankenexperiment introduces a collection of…
There is currently much interest in the development of improved trajectory-based methods for the simulation of nonadiabatic processes in complex systems. An important goal for such methods is the accurate calculation of the rate constant…
We shall revisit the conventional adiabatic or Markov approximation, showing its intrinsic failure in describing the proper quantum-mechanical evolution of a generic subsystem interacting with its environment. In particular, we shall show…
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…
In this work, we revisit the electron transfer rate theory, with particular interests in the distinct quantum solvation effect, and the characterizations of adiabatic/nonadiabatic and Markovian/non-Markovian rate processes. We first present…
Non-adiabatic decay rates for a radio-frequency dressed magnetic trap are calculated using Fermi's Golden Rule: that is, we examine the probability for a single atom to make transitions out of the dressed trap and into a continuum in the…
The Nonequilibrium Fermi's Golden Rule (NE-FGR) provides a convenient theoretical framework for calculating the charge transfer rate between a photoexcited bright donor electronic state and a dark acceptor electronic state, when the nuclear…