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The free energy of ion solvation can be decomposed into enthalpic and entropic contributions. This helps to understand the connection between the dielectric properties and the underlying forces. We present a simple linear-response model of…
We report microscopic calculations of free energies and entropies for intramolecular electron transfer reactions. The calculation algorithm combines the atomistic geometry and charge distribution of a molecular solute obtained from quantum…
A mixture of solvent particles with short-range, directional interactions and solute particles with short-range, isotropic interactions that can bond multiple times is of fundamental interest in understanding liquids and colloidal mixtures.…
Recent studies on the solvation of atomistic and nanoscale solutes indicate that a strong coupling exists between the hydrophobic, dispersion, and electrostatic contributions to the solvation free energy, a facet not considered in current…
We study the energy distribution in the extended resonant level model at equilibrium. Previous investigations [Phys. Rev. B {\bf 89}, 161306 (2014), Phys. Rev. B {\bf 93}, 115318 (2016)] have found, for a resonant electronic level…
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…
The Renyi entropy is a generalization of the usual concept of entropy which depends on a parameter q. In fact, Renyi entropy is closely related to free energy. Suppose we start with a system in thermal equilibrium and then suddenly divide…
Complex systems that are characterized by strong correlations and fat-tailed distribution functions have been argued to be incompatible within the framework of Boltzmann-Gibbs entropy. As an alternative, so-called generalized entropies were…
We present a method for computing free-energy differences using thermodynamic integration with a neural network potential that interpolates between two target Hamiltonians. The interpolation is defined at the sample distribution level, and…
A lower bound on the R\'enyi differential entropy of a sum of independent random vectors is demonstrated in terms of rearrangements. For the special case of Boltzmann-Shannon entropy, this lower bound is better than that given by the…
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.…
A system of interacting, identical fermions described by standard Landau Fermi-liquid (FL) theory can experience a rearrangement of its Fermi surface if the correlations grow sufficiently strong, as occurs at a quantum critical point where…
For many chemical processes the accurate description of solvent effects are vitally important. Here, we describe a hybrid ansatz for the explicit quantum mechanical description of solute-solvent and solvent-solvent interactions based on…
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…
The expression of the free energy of a liquid in terms of an explicit decomposition of the particle configurations into local coordination clusters is examined. We argue that the major contribution to the entropy associated with structural…
Following the paradigm of Boltzmann-BBGKY we propose a correlation entropy (of the nth order) for an interacting quantum field, obtained by `slaving' (truncation with causal factorization) of the higher (n+1 th) order correlation functions…
A central concept in the connection between physics and information theory is entropy, which represents the amount of information extracted from the system by the observer performing measurements in an experiment. Indeed, Jaynes' principle…
The laws of thermodynamics, despite their wide range of applicability, are known to break down when systems are correlated with their environments. Here, we generalize thermodynamics to physical scenarios which allow presence of…
We present an application of Flory-type self-consistent field theory of the flexible polymer chain dissolved in the binary mixture of solvents to theoretical description of co-nonsolvency. We show that our theoretical predictions are in…
We derive thermodynamically consistent models of reaction-diffusion equations coupled to a heat equation. While the total energy is conserved, the total entropy serves as a driving functional such that the full coupled system is a gradient…