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Electronic structures are fully determined by the exchange-correlation (XC) potential. In this work, we develop a new method to construct reliable XC potentials by properly mixing the exact exchange and the local density approximation…

Chemical Physics · Physics 2024-08-06 Chen Huang

A local permittivity model is proposed to accurately characterize spatial dispersion in non-local wire-medium (WM) structures with arbitrary terminations. A closed-form expression for the local thickness-dependent permittivity is derived…

Classical Physics · Physics 2020-04-22 Alexander B. Yakovlev , Mário G. Silveirinha , George W. Hanson

We derive an energy-based continuum limit for $\varepsilon$-graphs endowed with a general connectivity functional. We prove that the discrete energy and its continuum counterpart differ by at most $O(\varepsilon)$; the prefactor involves…

Numerical Analysis · Mathematics 2025-10-31 Yahong Yang , Sun Lee , Jeff Calder , Wenrui Hao

We present a microscopic theory of equilibrium solvation in solvents with zero dipole moment and non-zero quadrupole moment (quadrupolar solvents). The theory is formulated in terms of autocorrelation functions of the quadrupolar…

Statistical Mechanics · Physics 2009-11-11 Anatoli A. Milischuk , Dmitry V. Matyushov

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

Electrostatic correlations and variable permittivity of electrolytes are essential for exploring many chemical and physical properties of interfaces in aqueous solutions. We propose a continuum electrostatic model for the treatment of these…

Soft Condensed Matter · Physics 2015-06-23 Manman Ma , Zhenli Xu

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

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 is presented for first-principle simulations of charged colloidal dispersions in electrolyte solutions. Utilizing a smoothed profile for colloid-solvent boundaries, efficient mesoscopic simulations are enabled for…

Soft Condensed Matter · Physics 2007-05-23 Kang Kim , Ryoichi Yamamoto

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

A multispecies, collisionless plasma is modeled by the Vlasov-Poisson system. Assuming the plasma is neutral and the electric field decays with sufficient rapidity as $t \to\infty$, we show that solutions can be constructed with arbitrarily…

Analysis of PDEs · Mathematics 2025-02-06 Grace Mattingly , Stephen Pankavich , Jonathan Ben-Artzi

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

Methods for estimating the correlation energy of molecules and other electronic systems are discussed based on the assumption that the correlation energy can be partitioned between atomic regions. In one method, the electron density is…

Chemical Physics · Physics 2022-05-16 Jerry L. Whitten

Reliable first-principles calculations of electrochemical processes require accurate prediction of the interfacial capacitance, a challenge for current computationally-efficient continuum solvation methodologies. We develop a model for the…

Chemical Physics · Physics 2018-04-12 Ravishankar Sundararaman , Kendra Letchworth-Weaver , Kathleen Schwarz

Electrolyte solutions play critical role in a vast range of important applications, yet an accurate and scalable method of predicting their properties without fitting to experiment has remained out of reach, despite over a century of…

Chemical Physics · Physics 2024-11-18 Junji Zhang , Joshua Pagotto , Tim Gould , Timothy T. Duignan

Thermodynamic models present binary interaction parameters, based on the Boltzmann weight. Discrepancies from experimental data lead to empirically consider temperature dependence of the parameters, but these modifications keep unchanged…

Chemical Physics · Physics 2012-06-05 Ernesto P. Borges

This paper develops the so-called Weighted Energy-Dissipation (WED) variational approach for the analysis of gradient flows in metric spaces. This focuses on the minimization of the parameter-dependent global-in-time functional of…

Analysis of PDEs · Mathematics 2018-01-17 Riccarda Rossi , Giuseppe Savaré , Antonio Segatti , Ulisse Stefanelli

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.…

Chemical Physics · Physics 2019-02-01 Alejandro J. Garza

The increasing number of experimental observations on highly concentrated electrolytes and ionic liquids show qualitative features that are distinct from dilute or moderately concentrated electrolytes, such as self-assembly, multiple-time…

Chemical Physics · Physics 2018-02-08 Nir Gavish , Doron Elad , Arik Yochelis

A dielectric solvation model is applied to the prediction of the equilibrium ionization of liquid water over a wide range of density and temperature with the objective of calibrating that model for the study of ionization in water of…

chem-ph · Physics 2009-09-25 Gregory J. Tawa , Lawrence R. Pratt