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In the free energy of hydration of a solute, the chemical contribution is given by the free energy required to expel water molecules from the coordination sphere and the packing contribution is given by the free energy required to create…

Chemical Physics · Physics 2010-08-09 Valery Weber , Safir Merchant , Purushottam D. Dixit , D. Asthagiri

First steps towards developing a new perturbation theory for molecular liquids are taken. By choosing a new form of splitting the site-site potential functions between molecules, we will get a set of atomic fluids as the reference system…

Chemical Physics · Physics 2017-11-21 Mehrdad Khanpour

Liquid water is reluctant to lose hydrogen-bond coordination. Here we reveal that it also demands contraction and reorientation of the second molecular shell to compensate for coordination defects. Such molecular principle will be shown to…

Soft Condensed Matter · Physics 2024-08-27 Nicolás A. Loubet , Alejandro R. Verde , Gustavo A. Appignanesi

A recently developed statistical mechanical Quasi-Chemical Theory (QCT) has led to significant insights into solvation phenomena for both hydrophilic and hydrophobic solutes. The QCT exactly partitions solvation free energies into three…

Statistical Mechanics · Physics 2009-11-13 David M. Rogers , Thomas L. Beck

An `ab initio' molecular dynamics simulation of a Na+ ion in aqueous solution is presented and discussed. The calculation treats a Na+ ion and 32 water molecules with periodic boundary conditions on a cubic volume determined by an estimate…

Chemical Physics · Physics 2007-05-23 Susan B. Rempe , Lawrence R. Pratt

Second-harmonic scattering experiments of water and other bulk molecular liquids have long been assumed to be insensitive to interactions between the molecules. The measured intensity is generally thought to arise from incoherent scattering…

Soft Condensed Matter · Physics 2017-08-28 Gabriele Tocci , Chungwen Liang , David M. Wilkins , Sylvie Roke , Michele Ceriotti

The microscopic description of the local structure of water remains an open challenge. Here, we adopt an agnostic approach to understanding water's hydrogen bond network using data harvested from molecular dynamics simulations of an…

Soft Condensed Matter · Physics 2022-04-05 Adu Offei-Danso , Ali Hassanali , Alex Rodriguez

A direct measure of hydrogen bonding in water under conditions ranging from the normal state to the supercritical regime is derived from the Compton scattering of inelastically-scattered X-rays. First, we show that a measure of the number…

We investigated theoretically water evaporation from concentrated supramolecular mixtures, such as solutions of polymers or amphiphilic molecules, using numerical resolutions of a one dimensional model based on mass transport equations.…

Soft Condensed Matter · Physics 2017-10-25 Jean-Baptiste Salmon , Frédéric Doumenc , Béatrice Guerrier

A molecular theory of liquid water is identified and studied on the basis of computer simulation of the TIP3P model of liquid water. This theory would be exact for models of liquid water in which the intermolecular interactions vanish…

Chemical Physics · Physics 2009-11-13 J. K. Shah , D. Asthagiri , L. R. Pratt , M. E. Paulaitis

We show that phase separation can occur in a one-component liquid outside its coexistence curve (CX) with addition of a small amount of a solute. The solute concentration at the transition decreases with increasing the difference of the…

Soft Condensed Matter · Physics 2015-06-01 Ryuichi Okamoto , Akira Onuki

The high-energy tail of the distribution of solute-solvent interaction energies is poorly characterized for condensed systems, but this tail region is of principal interest in determining the excess free energy of the solute. We introduce…

Chemical Physics · Physics 2015-05-28 Valery Weber , Safir Merchant , D. Asthagiri

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

Many-body interactions in water are known to be important but difficult to treat in atomistic models and often are included only as a correction. Polarizable models treat them explicitly, with long-range many-body potentials, within their…

Chemical Physics · Physics 2023-02-21 David Abella , Giancarlo Franzese , Javier Hernández-Rojas

The vibrational motion of molecules in dissipative environments, such as solvation and protein molecules, is composed of contributions from both intermolecular and intramolecular modes. The existence of these collective modes introduces…

Soft Condensed Matter · Physics 2020-04-16 Seiji Ueno , Yoshitaka Tanimura

We present a family of alchemical perturbation potentials that enable the calculation of hydration free energies of small to medium-sized molecules in a concerted single alchemical coupling step instead of the commonly used sequence of two…

Quantitative Methods · Quantitative Biology 2021-02-24 Sheenam Khuttan , Solmaz Azimi , Joe Z. Wu , Emilio Gallicchio

Quantifying the statistics of occupancy of solvent molecules in the vicinity of solutes is central to our understanding of solvation phenomena. Number fluctuations in small `solvation shells' around solutes cannot be described within the…

Statistical Mechanics · Physics 2017-11-22 Purushottam D. Dixit , Artee Bansal , Walter G. Chapman , Dilip Asthagiri

In equilibrium and supercooled liquids, polymorphism is manifested by thermodynamic regions defined in the phase diagram, which are predominantly of different short- and medium-range order (local structure). It is found that on the phase…

Soft Condensed Matter · Physics 2024-03-19 Anatolii V. Mokshin , Roman V. Vlasov

The supra-molecular structure of a liquid is strongly connected to its dynamics which in turn controls macroscopic properties such as viscosity. Consequently, detailed knowledge about how this structure changes with temperature is essential…

Soft Condensed Matter · Physics 2025-08-05 Jan Philipp Gabriel , Robin Horstmann , Martin Tress

We examine the SPCE and TIP5P water models to study heat capacity effects associated with the hydrophobic hydration and interaction of Xenon particles. We calculate the excess chemical potential for Xenon employing the Widom particle…

Soft Condensed Matter · Physics 2007-05-23 Dietmar Paschek
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