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We propose a new model for estimating the free energy of forming a molecular cavity in a solvent, by assuming this energy is dominated by the electrostatic energy associated with creating the static (interface) potential inside the cavity.…

Chemical Physics · Physics 2020-05-28 Christopher D. Cooper , Jaydeep P. Bardhan

Employing a classical density-functional description of liquid environments, we introduce a rigorous method for the diffusion quantum Monte Carlo calculation of free energies and thermodynamic averages of solvated systems that requires…

Calculating free energy differences is a topic of substantial interest and has many applications including molecular docking and hydration, solvation, and binding free energies which is used in computational drug discovery. However, in…

Chemical Physics · Physics 2013-10-16 Asaf Farhi

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…

Chemical Physics · Physics 2025-10-28 Zhenyu Wang , Mira Todorova , Christoph Freysoldt , Jörg Neugebauer

Continuum solvation methods can provide an accurate and inexpensive embedding of quantum simulations in liquid or complex dielectric environments. Notwithstanding a long history and manifold applications to isolated systems in open boundary…

Materials Science · Physics 2014-12-02 Oliviero Andreussi , Nicola Marzari

The accurate prediction of solvation free energy is of significant importance as it governs the behavior of solutes in solution. In this work, we apply a variety of machine learning techniques to predict and analyze the alchemical free…

Chemical Physics · Physics 2024-11-11 Mingjun Han , Yukai Zhang , Taotao Yu , Guodong Du , ChiYung Yam , Ho-Kin Tang

Understanding lithium solvation and transport in ionic liquids is important due to their possible application in electrochemical devices. Using first-principles simulations aided by a metadynamics approach we study the free-energy landscape…

Chemical Physics · Physics 2017-08-07 Ali Kachmar , Marcelo Carignano , Teodoro Laino , Marcella Iannuzzi , Jürg Hutter

Treating water as a linearly responding dielectric continuum on molecular length scales allows very simple estimates of solvation structure and thermodynamics for charged and polar solutes. While this approach can successfully account for…

Statistical Mechanics · Physics 2021-07-07 Stephen J. Cox , Kranthi K. Mandadapu , Phillip L. Geissler

In this paper, we present an analytical solution to nonlocal continuum electrostatics for an arbitrary charge distribution in a spherical solute. Our approach relies on two key steps: (1) re-formulating the PDE problem using…

Chemical Physics · Physics 2012-08-22 Jaydeep P. Bardhan , Matthew G. Knepley , Peter R. Brune

Solvation in 1-ethyl-3-methylmidazolium chloride and in 1-ethyl-3-methylimidazolium hexafluorophosphate near equilibrium is investigated via molecular dynamics computer simulations with diatomic and benzenelike molecules employed as probe…

Soft Condensed Matter · Physics 2009-11-11 Y. Shim , M. Y. Choi , Hyung J. Kim

A methodology for calculating the contribution of charged defects to the configurational free energy of an ionic crystal is introduced. The temperature-independent Wang-Landau Monte Carlo technique is applied to a simple model of a solid…

Materials Science · Physics 2015-06-16 Robert M. Horton , Andrew J. Haslam , Amparo Galindo , George Jackson , Michael W. Finnis

We develop a computational method for modeling electrostatic interactions of arbitrarily-shaped, polarizable objects on colloidal length scales, including colloids/nanoparticles, polymers, and surfactants, dispersed in explicit ion…

Soft Condensed Matter · Physics 2024-06-18 Emily Krucker-Velasquez , James W. Swan , Zachary Sherman

We demonstrate that with two small modifications, the popular dielectric continuum model is capable of predicting, with high accuracy, ion solvation thermodynamics in numerous polar solvents, and ion solvation free energies in…

In this review we focus on the determination of phase diagrams by computer simulation with particular attention to the fluid-solid and solid-solid equilibria. The calculation of the free energy of solid phases using the Einstein crystal and…

Statistical Mechanics · Physics 2009-01-14 C. Vega , E. Sanz , J. L. F. Abascal , E. G. Noya

Molecular Density Functional Theory (MDFT) offers an efficient implicit- solvent method to estimate molecule solvation free-energies whereas conserving a fully molecular representation of the solvent. Even within a second order ap-…

Soft Condensed Matter · Physics 2014-06-12 Volodymyr P. Sergiievskyi , Guillaume Jeanmairet , Maximilien Levesque , Daniel Borgis

The long-ranged nature of the Coulomb potential requires a proper accounting for the influence of even distant electrostatic boundaries in the determination of the solvation free energy of a charged solute. We introduce an exact rewriting…

Statistical Mechanics · Physics 2019-05-01 Richard C. Remsing , John D. Weeks

The development of intense high-energy radiation sources and the improvement of techniques for detecting charged fragments have made possible experiments on multiple ionization of a molecule with registration of the momentum and charge of…

We present high-quality reference data for two fundamentally important groups of molecular properties related to a compound's utility as a lithium battery electrolyte. The first property is energy changes associated with charge excitations…

Sets of free energy differences are useful for finding the equilibria of chemical reactions, while absolute free energies have little physical meaning. However finding the relative free energy between two macrostates by subtraction of their…

Statistical Mechanics · Physics 2012-11-26 Joshua T. Berryman , Tanja Schilling

The Poisson-Boltzmann mean-field description of ionic solutions has been successfully used in predicting charge distributions and interactions between charged macromolecules. While the electrostatic model of charged fluids, on which the…

Soft Condensed Matter · Physics 2014-04-22 Dan Ben-Yaakov , David Andelman , Daniel Harries , Rudi Podgornik