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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

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…

Statistical Mechanics · Physics 2018-08-14 Stephen J. Cox , Phillip L. Geissler

The thesis focuses on the prediction of solvation thermodynamics using integral equation theories. Our main goal is to improve the approach using a rational correction. We achieve it by extending recently introduced pressure correction, and…

Chemical Physics · Physics 2017-04-19 Maksim Misin

Chemical thermodynamic models of solvent and solute activities predict the equilibrium behaviour of aqueous solutions. How-ever, these models are semi-empirical. They represent micro-scale ion and solvent behaviours that control the…

Chemical Physics · Physics 2022-01-26 Xiangwen Wang , Simon L. Clegg , Devis Di Tommaso

A solute-blocking model is presented that provides a kinetic explanation of osmosis and ideal solution thermodynamics. It validates a diffusive model of osmosis that is distinct from the traditional convective flow model of osmosis. Osmotic…

Biological Physics · Physics 2021-12-14 Peter Hugo Nelson

Twenty years ago Poole et al. (Nature 360, 324, 1992) suggested that the anomalous properties of supercooled water may be caused by a critical point that terminates a line of liquid-liquid separation of lower-density and higher-density…

Chemical Physics · Physics 2017-08-14 V. Holten , M. A. Anisimov

We study the evolution of dynamic fluctuations averaged over different space lengths and time scales to characterize spatially and temporally heterogeneous behavior of TIP4P/2005 water in liquid and supercooled states. Analysing a million…

State-of-the-art simulations of high-energy nuclear collisions rely on hybrid setups, involving in particular a pre-equilibrium stage to let the system evolve from a far-from-equilibrium initial condition towards a near-equilibrated state…

Nuclear Theory · Physics 2024-10-31 Nicolas Borghini , Renata Krupczak , Hendrik Roch

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

A new molecular simulation method for the calculation of vapour-liquid equilibria of mixtures is presented. In this method, the independent thermodynamic variables are temperature and liquid composition. In the first step, one isobaric…

Chemical Physics · Physics 2009-05-06 J. Vrabec , H. Hasse

The formation of biomolecular condensates inside cells often involve intrinsically disordered proteins (IDPs), and several of these IDPs are also capable of forming droplet-like dense assemblies on their own, through liquid-liquid phase…

Biological Physics · Physics 2020-02-26 Daniel Nilsson , Anders Irbäck

Entropy scaling is a powerful technique that has been used for predicting transport properties of pure components over a wide range of states. However, modeling mixture diffusion coefficients by entropy scaling is an unresolved task. We…

Chemical Physics · Physics 2026-04-03 Sebastian Schmitt , Hans Hasse , Simon Stephan

The size and composition distribution of an ensemble of aqueous organic droplets, evolving via nucleation and concomitant chemical aging, may be affected by the latent heat of condensation and enthalpy of heterogeneous chemical reactions,…

Atmospheric and Oceanic Physics · Physics 2022-01-11 Yuri S. Djikaev , Batradz I. Djikkaity

The thermodynamics of hydration changes gradually from entropic for small solutes to enthalpic for large ones. The small-to-large crossover lengthscale of hydrophobic hydration depends on the thermodynamic conditions of the solvent such as…

Soft Condensed Matter · Physics 2015-06-15 Yuri S. Djikaev , Eli Ruckenstein

Diffusivity, a measure for how rapidly a fluid self-mixes, shows an intimate, but seemingly fragmented, connection to thermodynamics. On one hand, the "configurational" contribution to entropy (related to the number of mechanically-stable…

Statistical Mechanics · Physics 2007-05-23 Jeetain Mittal , Jeffrey R. Errington , Thomas M. Truskett

We present a comprehensive theoretical study of finite size effects in the relaxation dynamics of glass-forming liquids. Our analysis is motivated by recent theoretical progress regarding the understanding of relevant correlation length…

Statistical Mechanics · Physics 2012-09-12 Ludovic Berthier , Giulio Biroli , Daniele Coslovich , Walter Kob , Cristina Toninelli

We numerically study the finite-size droplet condensation-evaporation transition in two dimensions. We consider and compare two orthogonal approaches, namely at fixed temperature and at fixed density, making use of parallel multicanonical…

Statistical Mechanics · Physics 2017-01-13 Andreas Nußbaumer , Johannes Zierenberg , Elmar Bittner , Wolfhard Janke

A thermodynamic model for a mixture of alkanethiol-coated nanoparticles (NPs) and low molecular weight (non-polymeric) solvent is developed, and calculations of liquid-liquid phase equilibrium for different values of NP core radius,…

Materials Science · Physics 2013-11-22 Ezequiel R. Soule , Cristina E. Hoppe , Julio Borrajo , Roberto J. J. Williams

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…

Clathrate hydrates are vital in energy research and environmental applications. Understanding their stability is crucial for harnessing their potential. In this work, we employ direct coexistence simulations to study finite-size effects in…

Soft Condensed Matter · Physics 2024-08-06 S. Blazquez , J. Algaba , J. M. Míguez , C. Vega , F. J. Blas , M. M. Conde
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