Related papers: Activation entropy of electron transfer reactions
Intermolecular charge transfer reactions are key processes in physical chemistry. The electron-transfer rates depend on a few system's parameters, such as temperature, electromagnetic field, distance between adsorbates and, especially, the…
This study considers electronic transitions within donor-acceptor complexes dissolved in media with macroscopic polarization. The change of the polarizability of the donor-acceptor complex in the course of electronic transition couples to…
The entropies of molecules in solution are routinely calculated using gas phase formulae. It is assumed that, because implicit solvation models are fitted to reproduce free energies, this is sufficient for modeling reactions in solution.…
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…
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…
Using the entropy $S$ as a reaction coordinate, we determine the free energy barrier associated with the formation of a liquid droplet from a supersaturated vapor for atomic and molecular fluids. For this purpose, we develop the $\mu VT-S$…
Microscopic formula to describe the entropy of biomolecular solutions are derived based on the Gibbs formula of entropy, and the generalized Langevin theory combined with the RISM/3D-RISM theory. Two formula are derived: one is concerned…
For a first principles understanding of macromolecular processes, a quantitative understanding of the underlying free energy landscape and in particular its entropy contribution is crucial. The stability of biomolecules, such as proteins,…
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…
Free energies play a central role in characterising the behaviour of chemical systems and are among the most important quantities that can be calculated by molecular dynamics simulations. Solvation free energies in various organic solvents,…
We report applications of analytical formalisms and Molecular Dynamics (MD) simulations to the calculation of redox entropy of plastocyanin metalloprotein in aqueous solution. The goal of our analysis is to establish critical components of…
Accurate calculations of solvation free energies remain a central challenge in molecular simulations, often requiring extensive sampling and numerous alchemical intermediates to ensure sufficient overlap between phase-space distributions of…
Molecular conduction operating in dielectric solvent environments are often described using kinetic rates based on Marcus theory of electron transfer at a molecule-metal electrode interface. However, the successive nature of charge transfer…
A new simulated tempering method, which is referred to as simulated tempering umbrella sampling, for calculating the free energy of chemical reactions is proposed. First principles molecular dynamics simulations with this simulated…
Using molecular simulation, we analyze the capillary condensation and evaporation processes for Argon confined in a cylindrical nanopore. For this purpose, we define the entropy of the adsorbed fluid as a reaction coordinate and determine…
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…
Understanding how different classes of molecules move across biological membranes is a prerequisite to predicting a solute's permeation rate, which is a critical factor in the fields of drug design and pharmacology. We use biased Molecular…
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…
Thermal activation of dislocations is critical for predicting the mechanical response of materials under common experimental conditions. According to transition state theory (TST), the rate for the system to overcome free energy barriers…
Quantum--Mechanical methods that are both computationally fast and accurate are not yet available for electronic excitations having charge transfer character. In this work, we present a significant step forward towards this goal for those…