相关论文: Analytic continuation of Wolynes theory into the M…

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…

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 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…

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 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…

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 show that the time dependent single electron, nuclear density matrix of an interacting electronic system coupled to nuclear degrees of freedom can be exactly reproduced by that of an electronic system with arbitrarily specified…

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 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…

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…

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…

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 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 semiclassical approximations to Green's functions of multidimensional systems, extending Gutzwiller's work to the classically forbidden region. Based on steepest-descent integrals over these functions, we derive an instanton…

An extension of the CCS-method [Chem. Phys. 2004, 304, p. 103-120] for simulating non-adiabatic dynamics with quantum effects of the nuclei is put forward. The time-dependent Schr\"{o}dinger equation for the motion of the nuclei is solved…

Fermi energies in fullerene compounds and cuprates are extremely small as consequence of the small number of charge carriers and are comparable to the phonon frequency scale. In this situation the conventional Migdal-Eliashberg theory does…

We derive a time-dependent master equation for an externally driven system whose subsystems weakly interact with each other and locally connect to the thermal reservoirs. The nonadiabatic equation obtained here can be viewed as a…

We show how the dynamically nonlocal formulation of classical nuclear motion in the presence of quantal electronic transitions presented many years ago by Pechukas can be localized in time using time dependent perturbation theory to give an…

Real-time simulations of laser-driven electron dynamics contain information about molecular optical properties through all orders in response theory. These properties can be extracted by assuming convergence of the power series expansion of…