Related papers: Instanton Theory for Nonadiabatic Tunneling throug…
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…
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…
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…
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…
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…
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…
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…
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…
Semiclassical instanton theory is a form of quantum transition-state theory which can be applied to computing thermal reaction rates for complex molecular systems including quantum tunneling effects. There have been a number of attempts to…
Instanton rate theory is used to study tunneling events in a wide range of systems including low-temperature chemical reactions. Despite many successful applications, the method has never been obtained from first principles, relying instead…
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…
Fermi's Golden Rule (FGR) is one of the most impactful formulas in quantum mechanics, providing a link between easy-to-measure observables - such as transition rates - and fundamental microscopic properties - such as density of states or…
We present a description of nuclear spontaneous fission, and generally of quantum tunneling, in terms of instantons - periodic imaginary-time solutions to time-dependent mean-field equations - that allows for a comparison with more familiar…
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…
Instanton theory has arisen as a practical tool for calculating tunneling splittings in molecular systems. Unfortunately, the original formulation of instanton theory fundamentally breaks down when trying to calculate the level splitting in…
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…
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…
A nonlinear Landau-Zener model was proposed recently to describe, among a number of applications, the nonadiabatic transition of a Bose-Einstein condensate between Bloch bands. Numerical analysis revealed a striking phenomenon that…
Marcus-Levich-Jortner (MLJ) theory is one of the most commonly used methods for including nuclear quantum effects into the calculation of electron-transfer rates and for interpreting experimental data. It divides the molecular problem into…