Related papers: An improved path-integral method for golden-rule r…
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 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…
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 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…
This dissertation unifies one of the central methods of classical rate calculation, `Transition-State Theory' (TST), with quantum mechanics, thereby deriving a rigorous `Quantum Transition-State Theory' (QTST). The resulting QTST is…
The aqueous ferrous-ferric system provides a classic example of an electron-transfer process in solution. There has been a long standing argument spanning more than three decades around the importance of nuclear tunnelling in this system,…
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…
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…
Fermi's golden rule (FGR) serves as the basis for many expressions of spectroscopic observables and quantum transition rates. The utility of FGR has been demonstrated through decades of experimental confirmation. However, there still remain…
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.…
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…
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…
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…
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…
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…
In Part I [J. Chem. Phys. 138, 084108 (2013)] we derived a quantum transition-state theory by taking the t->0+ (short-time) limit of a new form of quantum flux-side time-correlation function containing a ring-polymer dividing surface. This…
Fermi's golden rule is of great importance in quantum dynamics. However, in many textbooks on quantum mechanics, its contents and limitations are obscured by the approximations and arguments in the derivation, which are inevitable because…
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…
A scarcity of known chemical kinetic parameters leads to the use of many reaction rate estimates, which are not always sufficiently accurate, in the construction of detailed kinetic models. To reduce the reliance on these estimates and…