Related papers: Transition state redox during dynamical processes …
Transition State Theory is a central cornerstone in reaction dynamics. Its key step is the identification of a dividing surface that is crossed only once by all reactive trajectories. This assumption is often badly violated, especially when…
We derive an explict bias dependent expression for electron transfer reaction rate from a solvated redox to a electrode through a bridged molecule of arbitrary length. The interaction of the solvated redox with the solvent is modelled as a…
Non-equilibrium critical phenomena generally exist in many dynamic systems, like chemical reactions and some driven-dissipative {reactive} particle systems. Here, by using computer simulation and theoretical analysis, we demonstrate the…
Transition State Theory overestimates reaction rates in solution because conventional dividing surfaces between reagents and products are crossed many times by the same reactive trajectory. We describe a recipe for constructing a…
Numerous aqueous systems host elements in multiple redox states, with wide ranging implications such as their influence on the formation/dissolution of minerals, water toxicity, and nutrient cycling. To uncover governing mechanisms and…
Electrochemical devices often consist of multicomponent electrolyte solutions. Two processes influence the overall dynamics of these devices: the formation of electrical double layers and chemical conversion due to redox reactions. However,…
Chemical reactions subjected to time-varying external forces cannot generally be described through a fixed bottleneck near the transition state barrier or dividing surface. A naive dividing surface attached to the instantaneous, but moving,…
Understanding how the electronic structure of electrodes influences electrocatalytic reactions has been a longstanding topic in the electrochemistry community, with predominant attention paid to metallic electrodes. In this work, we present…
A Redox Flow Battery (RFB) is one of the promising energy storage systems in power grid. An RFB has many advantages such as a quick response, a large capacity, and a scalability. Due to these advantages, an RFB can operate in mixed time…
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,…
Describing Li-ion battery positive electrodes in terms of distinct transition metal or oxygen redox regimes can lead to confusion in understanding metal-ligand hybridisation, oxygen dimerisation, and degradation. There is a pressing need to…
Modern energy applications, especially electric vehicles, demand high energy batteries. However, despite decades of intensive efforts, the highest energy density and commercially viable batteries are still based on LiCoO2, the very first…
When a chemical reaction is driven by an external field, the transition state that the system must pass through as it changes from reactant to product -for example, an energy barrier- becomes time-dependent. We show that for periodic…
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…
Transition state calculation is a critical technique to understand and predict versatile dynamical phenomena in solids. However, the transition state results obtained at zero Kelvin are often utilized for prediction or interpretation of…
The accuracy of rate constants calculated using transition state theory depends crucially on the correct identification of a recrossing--free dividing surface. We show here that it is possible to define such optimal dividing surface in…
We investigate the transport characteristics of a redox system weakly coupled to leads in the Coulomb blockade regime. The redox system comprises a donor and acceptor separated by an insulating bridge in a solution. It is modeled by a…
Recently, we have shown that thermal effects play a crucial role in speeding up the rate of bond-dissociation reactions. This was done by applying a simple temperature-shifted Arrhenius Law to the experimental data, corroborated with…
We study diffusion-controlled processes in nonequilibrium steady states, where standard rate theory assumptions break down. Using transition path theory, we generalize the relations between reactive probability fluxes and measures of the…
The traditional concept of phase transitions has, in recent years, been widened in a number of interesting ways. The concept of a topological phase transition separating phases with a different ground state topology, rather than phases of…