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Estimating the free energy in molecular simulation requires, implicitly or explicitly, counting how many times the system is observed in a finite region. If the simulation is biased by an external potential, the weight of the configurations…

Chemical Physics · Physics 2021-12-22 Matteo Carli , Alessandro Laio

We present the theory and implementation of a Poisson-Boltzmann implicit solvation model for electrolyte solutions. This model can be combined with arbitrary electronic structure methods that provide an accurate charge density of the…

Computational Physics · Physics 2020-01-08 Christopher J. Stein , John M. Herbert , Martin Head-Gordon

Recent predictions of absolute binding free energies of host-guest complexes in aqueous solution using electronic structure theory have been encouraging for some systems, while other systems remain problematic for others. In paper I…

Chemical Physics · Physics 2015-03-11 Jan H. Jensen

We propose a nonlocal Poisson-Fermi model for ionic solvent that includes ion size effects and polarization correlations among water molecules in the calculation of electrostatic potential. It includes the previous Poisson-Fermi models as…

Chemical Physics · Physics 2016-08-03 Dexuan Xie , Jinn-Liang Liu , Bob Eisenberg , L. Ridgway Scott

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…

Statistical Mechanics · Physics 2025-03-26 Bálint Máté , François Fleuret , Tristan Bereau

Closed-form, analytical approximations for electrostatic properties of molecules are of unique value, as these can provide computational speed, versatility, and physical insight. Here, we derive a simple, closed-form formula for the…

Chemical Physics · Physics 2022-03-14 Dan Folescu , Alexey V. Onufriev

Integral equation theory of molecular liquids based on statistical mechanics is quite promising as an essential part of multiscale methodology for chemical and biomolecular nanosystems in solution. Beginning with a molecular interaction…

Soft Condensed Matter · Physics 2015-10-23 A. Kovalenko

We derive an equation capable of treating both the electrostatic and non-electrostatic interactions in the charged liquids. The equation derived is a complex version of the Poisson-Boltzmann equation, in which the non-electrostatic…

Soft Condensed Matter · Physics 2025-02-12 Li Wan

The accurate prediction of solvation free energies is critical for understanding various phenomena in the liquid phase, including reaction rates, equilibrium constants, activity coefficients, and partition coefficients. Despite extensive…

A numerical method using implicit surface representations is proposed to solve the linearized Poisson-Boltzmann equations that arise in mathematical models for the electrostatics of molecules in solvent. The proposed method used an implicit…

Numerical Analysis · Mathematics 2018-04-04 Yimin Zhong , Kui Ren , Richard Tsai

We present a method to search low energy configurations of polar molecules in the complex potential energy surfaces associated with dense fluids. The search is done in the configurational space of the translational and rotational degrees of…

Chemical Physics · Physics 2016-09-08 Gianni De Fabritiis , Rafael Delgado-Buscalioni , Peter V. Coveney

The issues of electronic polarizability in molecular dynamics simulations are discussed. We argue that the charges of ionized groups in proteins, and charges of ions in conventional non-polarizable force fields such as CHARMM, AMBER,…

Chemical Physics · Physics 2017-09-13 Igor Leontyev , Alexei Stuchebrukhov

We study alchemical atomic energy partitioning as a method to estimate atomisation energies from atomic contributions which are defined in physically rigorous and general ways through use of the uniform electron gas as a joint reference. We…

We consider a set of electrostatic problems relevant for determining the real-space structure and the ground-state energy of a two-dimensional electron liquid subject to smooth external potentials. Three fundamental geometries are…

Mesoscale and Nanoscale Physics · Physics 2007-05-23 M. M. Fogler

Free energy calculations are widely used tools in computational chemistry, but their dependence on the assignment of partial charges during force field parametrization reduces their accuracy and reproducibility. In this work, we highlight…

We investigate the dissociation and ionization equilibria of deuterium fluid over a wide range of temperatures and densities. The partition functions for molecular and atomic species are evaluated, in a statistical-mechanically consistent…

Plasma Physics · Physics 2015-11-19 Mofreh R. Zaghloul

We propose a new method to compute the free energy or enthalpy of fluids or disordered solids by computer simulation . The main idea is to construct a reference system by freezing one representative configuration, and then carry out a…

Computational Physics · Physics 2011-03-16 Friederike Schmid , Tanja Schilling

Vortices in electron fluids are a key indicator of electron hydrodynamics. However, a comprehensive framework linking macroscopic vorticity measurements with microscopic interactions and scattering mechanisms has been lacking. We employ…

Mesoscale and Nanoscale Physics · Physics 2024-09-27 Khachatur G. Nazaryan , Leonid Levitov

We present a method to derive implicit solvent models of electrolyte solutions from all-atom descriptions; providing analytical expressions of the thermodynamic and structural properties of the ions consistent with the underlying explicit…

Chemical Physics · Physics 2010-01-18 J. J. Molina , J. -F. Dufreche , M. Salanne , O. Bernard , M. Jardat , P. Turq

Implicit electron-density solvation models based on joint density-functional theory offer a computationally efficient solution to the problem of calculating thermodynamic quantities of solvated systems from firstprinciples quantum…

Chemical Physics · Physics 2015-02-12 Deniz Gunceler , T. A. Arias