相关论文: Extending non-adiabatic rate theory to strong elec…

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…

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…

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 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 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…

The Marcus theory expression for the rate of non-adiabatic electron transfer is widely used across a range of physical conditions. Although Marcus theory defines the reorganization energy classically, here we show that the reorganization…

With the rapid development of nanophotonics and cavity quantum electrodynamics, there has been growing interest in how confined electromagnetic fields modify fundamental molecular processes such as electron transfer. In this paper, we…

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…

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…

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…

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…

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 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…

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 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 evaluate various analytical models for the electron-ion energy transfer and compare the results to data from molecular dynamics (MD) simulations. The models tested includes energy transfer via strong binary collisions, Landau-Spitzer…

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…

We examine electron transfer between two quantum states in the presence of a dissipative environment represented as a set of independent harmonic oscillators. For this simple model, the Marcus transfer rates can be derived and we show that…

We study nonadiabatic electron transfer within the biased spin-boson model. We calculate the incoherent transfer rate in analytic form at all temperatures for a power law form of the spectral density of the solvent coupling. In the Ohmic…