相关论文: On the calculation of quantum mechanical electron …
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…
The microscopic theory of chemical reactions is based on transition state theory, where atoms or ions transfer classically over an energy barrier, as electrons maintain their ground state. Electron transfer is fundamentally different and…
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…
Outer sphere electron transfer rates can be calculated from simulation data by sampling the equilibrium statistics of the canonical reaction coordinate -- the vertical energy gap. For these calculations, electron transfer is typically…
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 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 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 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 study the energy-transfer rate for electrons in a double-quantum-well structure, where the layers are coupled through screened Coulomb interactions. The energy-transfer rate between the layers (similar to the Coulomb drag effect in which…
The use of ring polymer molecular dynamics (RPMD) for the direct simulation of electron transfer (ET) reaction dynamics is analyzed in the context of Marcus theory, semiclassical instanton theory, and exact quantum dynamics approaches. For…
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…
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…
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…
We present a theory for the rate of energy exchange between electrons and ions -- also known as the electron-ion coupling factor -- in physical systems ranging from hot solid metals to plasmas, including liquid metals and warm dense matter.…
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…
A non-empirical exchange functional based on an interpolation between two limits of electron density: slowly varying limit and asymptotic limit, is proposed. In the slowly varying limit, we follow the study by Kleinman in 1984 which…
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…
Quantum rate theory encompasses the electron-transfer rate constant concept of electrochemical reactions as a particular setting, besides demonstrating that the electrodynamics of these reactions obey relativistic quantum mechanical rules.…
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…