相关论文: System size dependence of hydration shell occupanc…
Equilibrium properties of hydrogen-helium mixtures under thermodynamic conditions found in the interior of giant gas planets are studied by means of density functional theory molecular dynamics simulations. Special emphasis is placed on the…
We evaluate the relaxation time to equilibrium, and especially show that it is almost independent from the system size for macroscopic isolated quantum systems. It at most polynomially depends on the system size. This estimation holds when…
Water near hydrophobic surfaces is like that at a liquid-vapor interface, where fluctuations in water density are substantially enhanced compared to that in bulk water. Here we use molecular simulations with specialized sampling techniques…
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…
Hydrophobic hydration plays a crucial role in self-assembly processes over multiple length-scales, but the extrapolation of molecular-scale models to larger length-scale hydration phenomena is sometimes not warranted. Scaled-particle…
Quasi-chemical theory is utilized to analyze the roles of solute polarization and size in determining the structure and thermodynamics of bulk anion hydration for the Hofmeister series Cl$^-$, Br$^-$, and I$^-$. Excellent agreement with…
The structure of polydisperse hard sphere fluids, in the presence of a wall, is studied by the Rosenfeld density functional theory. Within this approach, the local excess free energy depends on only four combinations of the full set of…
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…
Amphiphiles are molecules which have both hydrophilic and hydrophobic parts. In water- and/or oil-like solvent, they self-assemble into extended sheet-like structures due to the hydrophobic effect. The free energy of an amphiphilic system…
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…
We examine the dependence of a thermodynamic potential of a fluid on the geometry of its container. If motion invariance, continuity, and additivity of the potential are fulfilled, only four morphometric measures are needed to describe…
This paper organizes McMillan-Mayer theory, the potential distribution approach, and quasi-chemical theory to provide theory for the thermodynamic effects associated with longer spatial scales involving longer time scales, thus helping to…
We introduce and test via molecular simulation a simple model for predicting the manner in which interparticle interactions and thermodynamic conditions impact the single-particle free-volume distributions of equilibrium fluids. The model…
Hydrophobic interactions are central to biological self-assembly and soft matter organization, yet their microscopic origins remain debated. A key hallmark is the strengthening of attraction between hydrophobic solutes with increasing…
A typical linear open system is often defined as a component of a larger conservative one. For instance, a dielectric medium, defined by its frequency dependent electric permittivity and magnetic permeability is a part of a conservative…
The entropy per particle in most Monte-Carlo simulations is size dependent due to correlated energy fluctuations. Guided by nanothermodynamics, we find a constraint for the Ising model that enhances the fluctuations and lowers the free…
Complexity Theory is highly interdisciplinary, therefore any regularities must hold on all levels of organization, independent on the nature of the system. An open question in science is how complex systems self-organize to produce emergent…
Hydrophobic interactions provide driving forces for protein folding, membrane formation, and oil-water separation. Motivated by information theory, the poorly understood nonpolar solute interactions in water are investigated. A simple…
We study the influence of the relative size of the reservoir on the adsorption isotherms of a fluid in disordered or inhomogeneous mesoporous solids. We consider both an atomistic model of a fluid in a simple, yet structured pore, whose…
We have developed a method to calculate the hydration of hydrophobic solutes by the fundamental measure theory. This method allows us to carry out calculations of the density profile and the hydration energy for hydrophobic molecules. An…