Related papers: A Molecular Density Functional Theory Approach to …
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).…
Electron transfer (ET) at electrochemical interfaces is central to energy conversion and storage, yet its theoretical and computational modeling remain active research areas. This review elucidates key concepts and theories of ET kinetics,…
Liquid states theories have emerged as a numerically efficient alternative to costly molecular dynamics simulations of electron transfer reactions in solution. In a recent paper [Chem. Sci., 2019, 10, 2130], we introduced the framework to…
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…
Solvation effect might have a tremendous influence on chemical reactions. However, precise quantum chemistry calculations are most often done either in vacuum neglecting the role of the solvent or using continuum solvent model ignoring its…
Classical density-functional theory provides an efficient alternative to molecular dynamics simulations for understanding the equilibrium properties of inhomogeneous fluids. However, application of density-functional theory to multi-site…
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…
Electron transfer (ET) at molecule-metal or molecule-semiconductor interfaces is a fundamental reaction that underlies all electro-chemical and molecular electronic processes as well as substrate-mediated surface photochemistry. In this…
The Marcus theory expression for the rate of non-adiabatic electron transfer is widely used across a range of physical conditions. Although Marcus theory defines the reorganization energy classically, here we show that the reorganization…
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…
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 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 introduce a new form of density functional theory for the {\em ab initio} description of electronic systems in contact with a molecular liquid environment. This theory rigorously joins an electron density-functional for the electrons of…
The effect of solvation on the electron transfer (ET) rate processes is investigated on the basis of the exact theory constructed in J. Phys. Chem. B Vol. 110, (2006); quant-ph/0604071. The nature of solvation is studied in a close relation…
We suggest to include the density of electron charge explicitly in the electron potential of density functional theory, rather than implicitly via exchange-correlation functionals. The advantages of the approach are conceptual and…
A classical density functional theory is applied to study solvation of solutes in water. An approx- imate form of the excess functional is proposed for water. This functional requires the knowledge of pure solvent direct correlation…
Density Functional Theory (DFT) is one of the most widely used methods for "ab initio" calculations of the structure of atoms, molecules, crystals, surfaces, and their interactions. Unfortunately, the customary introduction to DFT is often…
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 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…
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…