Related papers: A general non-adiabatic quantum instanton approxim…
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 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…
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…
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 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…
Ab initio instanton rate theory is a computational method for rigorously including tunnelling effects into calculations of chemical reaction rates based on a potential-energy surface computed on the fly from electronic-structure theory.…
Reactions involving adsorbates on metallic surfaces and impurities in bulk metals are ubiquitous in a wide range of technological applications. The theoretical modelling of such reactions presents a formidable challenge for theory because…
The Wolynes theory of electronically nonadiabatic reaction rates [P. G. Wolynes, J. Chem. Phys. 87, 6559 (1987)] is based on a saddle point approximation to the time integral of a reactive flux autocorrelation function in the nonadiabatic…
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…
We explore the relation between the quantum and semiclassical instanton approximations for the reaction rate constant. From the quantum instanton expression, we analyze the contributions to the rate constant in terms of minimum-action paths…
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…
Ring-polymer instanton theory has been developed to simulate the quantum dynamics of molecular systems at low temperatures. Chemical reaction rates can be obtained by locating the dominant tunneling pathway and analyzing fluctuations around…
A general method for the direct evaluation of the temperature dependence of the quantum-mechanical reaction rate constant in many-dimensional systems is described. The method is based on the quantum instanton approximation for the rate…
Adiabatic state engineering is a powerful technique in quantum information and quantum control. However, its performance is limited by the adiabatic theorem of quantum mechanics. In this scenario, shortcuts to adiabaticity, such as provided…
High-fidelity qubit initialization is of significance for efficient error correction in fault tolerant quantum algorithms. Combining two best worlds, speed and robustness, to achieve high-fidelity state preparation and manipulation is…
At present, several models for quantum computation have been proposed. Adiabatic quantum computation scheme particularly offers this possibility and is based on a slow enough time evolution of the system, where no transitions take place. In…
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…
The quantum speed limit specifies a universal bound of the fidelity between the initial state and the time-evolved state. We apply this method to find a bound of the fidelity between the adiabatic state and the time-evolved state. The bound…