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Many important applications of electronic structure methods involve molecules or solid surfaces in a solvent medium. Since explicit treatment of the solvent in such methods is usually not practical, calculations often employ continuum…

Chemical Physics · Physics 2015-02-12 Ravishankar Sundararaman , William A. Goddard

Continuum solvation models enable efficient first principles calculations of chemical reactions in solution, but require extensive parametrization and fitting for each solvent and class of solute systems. Here, we examine the assumptions of…

Chemical Physics · Physics 2014-10-10 Ravishankar Sundararaman , Deniz Gunceler , T. A. Arias

Solvation free energy is an important quantity in Computational Chemistry with a variety of applications, especially in drug discovery and design. The accurate prediction of solvation free energies of small molecules in water is still a…

Biological Physics · Physics 2007-05-23 A. Hildebrandt , O. Kohlbacher , R. Blossey , H. -P. Lenhof

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…

Statistical Mechanics · Physics 2009-11-11 J. Dzubiella , J. M. J. Swanson , J. A. McCammon

Theories of solvation free energies often involve electrostatic potentials at the position of a solute charge. Simulation calculations that apply cutoffs and periodic boundary conditions based on molecular centers result in center-dependent…

Chemical Physics · Physics 2008-02-03 Gerhard Hummer , Lawrence R. Pratt , Angel E. Garcia , Bruce J. Berne , Steven W. Rick

This paper determines the excess free energy associated with the formation of a spherical cavity in a hard sphere fluid. The solvation free energy can be calculated by integration of the structural changes induced by inserting the cavity…

Statistical Mechanics · Physics 2009-11-10 Yng-gwei Chen , John D. Weeks

We have developed and implemented an implicit electrolyte model in the Vienna Ab initio Simulation Package (VASP) that includes nonlinear dielectric and ionic responses as well as a nonlocal definition of the cavities defining the spatial…

Chemical Physics · Physics 2023-09-15 S M Rezwanul Islam , Foroogh Khezeli , Stefan Ringe , Craig Plaisance

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…

Classical density-functional theory is the most direct approach to equilibrium structures and free energies of inhomogeneous liquids, but requires the construction of an approximate free-energy functional for each liquid of interest. We…

Soft Condensed Matter · Physics 2014-10-10 Ravishankar Sundararaman , Kendra Letchworth-Weaver , T A Arias

We construct a new phase-field model for the solvation of charged molecules with a variational implicit solvent. Our phase-field free-energy functional includes the surface energy, solute-solvent van der Waals dispersion energy, and…

Numerical Analysis · Mathematics 2017-12-07 Yanxiang Zhao , Yanping Ma , Hui Sun , Bo Li , Qiang Du

We present the results of numerical simulations of fluctuations of the electrostatic potential and electric field inside cavities created in the fluid of dipolar hard spheres. We found that the thermodynamics of polar solvation dramatically…

Chemical Physics · Physics 2009-11-13 Daniel R. Martin , Dmitry V. Matyushov

We propose a systematic, {\em a priori} approach to the problem of the calculation of solvation energies using continuum dielectric models coupled to quantum mechanical description of reacting molecules. Our method does not rely on…

Materials Science · Physics 2007-05-23 Sohrab Ismail-Beigi , T. A. Arias , Phillip Marrone , Matthew Reagan , Jefferson W. Tester

In this thesis we study the lateral electrostatic interaction between a pair of non-identical, moderately charged colloidal particles trapped at an electrolyte interface in the limit of short inter-particle separations. Using a simplified…

Soft Condensed Matter · Physics 2017-10-17 Timo Schmetzer

In this paper we propose a nonlinear elasticity model of macromolecular conformational change (deformation) induced by electrostatic forces generated by an implicit solvation model. The Poisson-Boltzmann equation for the electrostatic…

Analysis of PDEs · Mathematics 2010-01-12 Yongcheng Zhou , Michael Holst , James Andrew McCammon

We devise a nonlocal correlation energy functional that describes the entire range of dispersion interactions in a seamless fashion using only the electron density as input. The new functional is considerably simpler than its predecessors…

Chemical Physics · Physics 2010-12-27 Oleg A. Vydrov , Troy Van Voorhis

The calculation of the solvation properties of a single water molecule in liquid water is carried out in two ways. In the first, the water molecule is placed in a cavity and the solvent is treated as a dielectric continuum. This model is…

chem-ph · Physics 2008-02-03 Steven W. Rick , B. J. Berne

A nematic liquid-crystal cell subject to an electric field created by electrodes held at constant potential is modeled as a variable capacitor in an RC circuit. The state of the system is characterized in terms of the director field in the…

Soft Condensed Matter · Physics 2021-07-13 Eugene C. Gartland

In the molecular dynamics calculations for the free energy of ions and ionic molecules, we often encounter wet charged molecular systems where electrical neutrality condition is broken. This causes a problem in the evaluation of…

Biological Physics · Physics 2020-07-15 Ryo Urano , Wataru Shinoda , Noriyuki Yoshii , Susumu Okazaki

We propose a predictive Density Functional Theory (DFT) for the calculation of solvation free energies. Our approach is based on a Helmholtz free-energy functional that is consistent with the perturbed-chain SAFT (PC-SAFT) equation of…

Chemical Physics · Physics 2021-07-07 Johannes Eller , Tanja Matzerath , Thijs van Westen , Joachim Gross

We modelled the aqueous solvation of a nonpolar solute as a function of the radius, temperature and pressure. In this study a simple two-dimensional Mercedes-Benz (MB) water model was used in NPT Monte Carlo simulations. This model has…

Soft Condensed Matter · Physics 2021-10-12 T. Urbic
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