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Liquid state theories such as integral equations and classical density functional theory often overestimate the bulk pressure of fluids because they require closure relations or truncations of functionals. Consequently, the cost to create a…

化学物理 · 物理学 2020-07-16 Anton Robert , Sohvi Luukkonen , Maximilien Levesque

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…

计算物理 · 物理学 2011-03-16 Friederike Schmid , Tanja Schilling

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…

软凝聚态物质 · 物理学 2015-10-23 A. Kovalenko

Quantitative prediction of thermodynamic properties in solution is essential for translating atomistic simulations into reliable chemical insight. As an exemplar system, the behaviour of CaCO$_3$ in water has been widely studied to…

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.…

化学物理 · 物理学 2019-02-01 Alejandro J. Garza

This report details an approach to improve the accuracy and precision of free energy difference estimates using thermodynamic integration data (slope of the free energy with respect to the switching variable lambda) and its application to…

计算物理 · 物理学 2010-01-19 Conrad Shyu , F. Marty Ytreberg

Predictive synthesis of aqueous organic solutions with desired liquid-solid phase equilibria could drive progress in industrial chemistry, cryopreservation, and beyond, but is limited by the predictive power of current solution…

材料科学 · 物理学 2024-11-28 Spencer P. Alliston , Chris Dames , Matthew J. Powell-Palm

Liquid states theories have emerged as a numerically efficient alternative to costly molecular dynamics simulations of electron transfer reactions in solution. In a recent paper [Chem. Sci., 2019, 10, 2130], we introduced the framework to…

化学物理 · 物理学 2021-04-14 Tzu-Yao Hsu , Guillaume Jeanmairet

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…

Solvation free energies are efficiently predicted by molecular density functionnal theory (MDFT) if one corrects the overpressure introduced by the usual homogeneous reference fluid approximation. Sergiievskyi et al. [Sergiievskyi et al.,…

Application of integral equation theory to complex fluids is reviewed, with particular emphasis to the effects of polydispersity and anisotropy on their structural and thermodynamic properties. Both analytical and numerical solutions of…

软凝聚态物质 · 物理学 2011-12-23 Domenico Gazzillo , Achille Giacometti

The determination of the solvation free energy of ions and molecules holds profound importance across a spectrum of applications spanning chemistry, biology, energy storage, and the environment. Molecular dynamics simulations are a powerful…

介观与纳米尺度物理 · 物理学 2023-11-28 Zhou Yu , Enrique R. Batista , Ping Yang , Danny Perez

Inferring properties of macroscopic solutions from molecular simulations is complicated by the limited size of systems that can be feasibly examined with a computer. When long-ranged electrostatic interactions are involved, the resulting…

统计力学 · 物理学 2018-08-14 Stephen J. Cox , Phillip L. Geissler

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…

化学物理 · 物理学 2015-02-12 Deniz Gunceler , T. A. Arias

Einstein's equations of General Relativity form a highly nonlinear system, so most exact solutions rely on symmetry assumptions. Spherically symmetric spacetimes have been particularly important, providing a tractable yet physically rich…

广义相对论与量子宇宙学 · 物理学 2026-01-08 Salvador Mengual

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…

材料科学 · 物理学 2014-12-02 Oliviero Andreussi , Nicola Marzari

This paper tests a dielectric model for variation of hydration free energy with geometry of complex solutes in water. It works out some basic aspects of the theory of boundary integral methods for these problems. One aspect of the…

chem-ph · 物理学 2008-02-03 L. R. Pratt , G. J. Tawa , G. Hummer , A. E. Garcia , S. A. Corcelli

The predictive electrolyte model COSMO-RS-ES is refined to improve the description of systems at 25{\deg}C in which strong ion pairing is expected due to a low static permittivity of the liquid phase. Furthermore, the short-range ion energy…

The spatial resolution of extensive thermodynamic functions is discussed. A physical definition of the spatial resolution based on a spatial analogy of partial molar quantities is advocated, which is shown to be consistent with how…

统计力学 · 物理学 2024-08-27 Rasmus A. X. Persson

Recent developments in molecular theories and simulation of ions and polar molecules in water are reviewed. The hydration of imidazole and imidazolium solutes is used to exemplify the theoretical issues. The treatment of long-ranged…

化学物理 · 物理学 2016-09-28 Gerhard Hummer , Lawrence R. Pratt , Angel E. Garcia
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