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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 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…
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…
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…
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).…
Biredox ionic liquids are a new class of functionalized electrolytes that may play an important role in future capacitive energy storage devices. By allowing additional storage of electrons inside the liquids, they can improve device…
The microscopic theory of chemical reactions is based on transition state theory, where atoms or ions transfer classically over an energy barrier, as electrons maintain their ground state. Electron transfer is fundamentally different and…
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 have reexamined the thermally induced Co(NH_3)_6^{2+/3+} [Co(II/III)] redox reaction using the first principles density-functional-theory method, semiclassical Marcus theory, and known charge transfer parameters. We confirm a previously…
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…
Electron transfer processes are ubiquitous in chemistry and of great importance in many systems of biological and commercial interest. The ab-initio description of these processes remains a challenge in theoretical chemistry, partly due to…
We consider electron transfer from a redox to an electrode through and adsorbed intermediate. The formalism is developed to cover all regimes of coverage factor, from lone adsorbate to monolayer regime. The randomness in the distribution of…
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.…
Interfacial charge transfer is widely assumed to obey Butler-Volmer kinetics. For certain liquid-solid interfaces, Marcus-Hush-Chidsey theory is more accurate and predictive, but it has not been applied to porous electrodes. Here we report…
Recent theoretical advances, based on a combination of concepts from Thouless' topological theory of adiabatic charge transport and a newly introduced gauge-invariance principle for transport coefficients, have permitted to connect (and…
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…
Accurate description of nonadiabatic dynamics of molecules at metal surfaces involving electron transfer has been a longstanding challenge for theory. Here, we tackle this problem by first constructing high-dimensional neural network…
The cross-exchange electron transfer expression arising from Marcus theory is deduced using Onsager's non-equilibrium Thermodynamics formalism.
Redox molecular junctions are molecular conduction junctions that involve more than one oxidation state of the molecular bridge. This property is derived from the ability of the molecule to transiently localize transmitting electrons,…
The interaction between molecular (atomic) electron(s) and the vacuum field of a reflective cavity generates a significant interest thanks to the rapid developments in nanophotonics. Such interaction which lies within the realm of cavity…