Related papers: Effective quantum reorganization energy for electr…
Marcus theory famously predicts that electron-transfer rates decrease once the thermodynamic driving force exceeds the reorganization energy. Yet many systems instead exhibit Rehm-Weller kinetics, in which the rate saturates rather than…
Marcus theory is fundamental to describing electron transfer reactions and quantifying their rates, effectively representing the energy surface associated with an electron transfer from the reactant to the product ionic state via parabolas…
Electron transfer (ET) reactions underpin energy conversion and chemical transformations in both biological and abiological systems. The efficiency of any ET process relies on achieving a desired ET rate within an optimal driving force…
In the pioneering work by R. A. Marcus, the solvation effect on electron transfer (ET) processes was investigated, giving rise to the celebrated nonadiabatic ET rate formula. In this work, on the basis of the thermodynamic solvation…
The cross-exchange electron transfer expression arising from Marcus theory is deduced using Onsager's non-equilibrium Thermodynamics formalism.
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…
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…
Electron Transfer (ET) reactions are modeled by the dynamics of a quantum two-level system (representing the electronic state) coupled to a thermalized bath of classical harmonic oscillators (representing the nuclei degrees of freedom).…
The Marcus theory of electron transfer assumes that diabatic energy gaps are sampled from a single ensemble. This assumption can break down in spatially anisotropic environments, such as Faradaic reactions at electrochemical interfaces,…
A general approach to calculate the diabatic surfaces for electron-transfer reactions is presented, based on first-principles molecular dynamics of the active centers and their surrounding medium. The excitation energy corresponding to the…
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 use a numerically exact real-time path integral Monte Carlo scheme to compute electron transfer dynamics between two redox sites within a spin-boson approach. The case of asymmetric reactions is studied in detail in the least understood…
In this work, we revisit the electron transfer rate theory, with particular interests in the distinct quantum solvation effect, and the characterizations of adiabatic/nonadiabatic and Markovian/non-Markovian rate processes. We first present…
Electron transfer organic reaction rates are considered employing the classic physical picture of Marcus wherein the heats of reaction are deposited as the energy of low frequency mechanical oscillations of reconfigured molecular positions.…
Beyond the dielectric continuum description initiated by Marcus theory, the nowadays standard theoretical approach to study electron transfer (ET) reactions in solution or at interfaces is to use classical force field or ab initio Molecular…
A nonperturbative electron transfer rate theory is developed based on the reduced density matrix dynamics, which can be evaluated readily for the Debye solvent model without further approximation. Not only does it recover for reaction rates…
It has been shown that both the electron-transfer rate constant of an electrochemical reaction and the conductance quantum are correlated with the concept of quantum capacitance. This simple association between the two separate concepts has…
Electron transfer is an important and fundamental process in chemistry, biology and physics, and has received significant attention in recent years. Perhaps one of the most intriguing questions concerns with the realization of the…
A comprehensive description of molecular electron transfer reactions is essential for our understanding of fundamental phenomena in bio-energetics and molecular electronics. Experimental studies of molecular systems in condensed-phase…
The rate of electron transfer between a molecular species and a metal, each at a different local temperature, is examined theoretically through implementation of a bithermal (characterized by two temperatures) Marcus formalism. Expressions…