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In fluids, the compressibility and related thermodynamic properties can be obtained from Kirkwood–Buff integrals (KBIs), i.e., infinite volume integrals over the radial distribution function (RDF). KBI theory has never been applied to crystals because the KBIs diverge when computed in the standard way as running integrals. Here, we show that KBI theory can be applied to solids without divergence, provided that the recently developed finite volume KBI method is used. In order to accelerate the integral convergence as a function of system size, we introduce a physically motivated convolution of the RDF. When using the convoluted RDF and an extrapolation of the finite-volume KBI, the zero-temperature KBI converges very fast to the exact value. We apply the theory to solid argon at finite temperatures. The RDF is computed with a Lennard-Jones potential using Monte Carlo and molecular dynamics simulations, and the isothermal compressibility κT is obtained from the KBI. The variation of κT with temperature agrees very well with experiment. The absolute value of κT is, however, underestimated by 40%–50%, which is attributed to finite size effects of the RDF obtained from molecular simulation. The error can be corrected by a single scaling factor that can be easily calculated at zero temperature. By extending Kirkwood–Buff solution theory to solids, this work lays a new framework for the thermodynamic modeling of complex structures, alloys, and solid solutions. [ABSTRACT FROM AUTHOR]

The adsorption of carbon monoxide and nitrogen molecules at the surface of four forms of solid water is investigated by means of grand canonical Monte Carlo simulations. The trapping ability of crystalline Ih and low-density amorphous ices, along with clathrate hydrates of structures I and II, is compared at temperatures relevant for astrophysics. It is shown that when considering a gas phase that contains mixtures of carbon monoxide and nitrogen, the trapping of carbon monoxide is favored with respect to nitrogen at the surface of all solids, irrespective of the temperature. The results of the calculations also indicate that some amounts of molecules can be incorporated in the bulk of the water structures, and the molecular selectivity of the incorporation process is investigated. Again, it is shown that incorporation of carbon monoxide is favored with respect to nitrogen in most of the situations considered here. In addition, the conclusions of the present simulations emphasize the importance of the strength of the interactions between the guest molecules and the water network. They indicate that the accuracy of the corresponding interaction potentials is a key point, especially for simulating clathrate selectivity. This highlights the necessity of having interaction potential models that are transferable to different water environments. [ABSTRACT FROM AUTHOR]

We present a new molecular simulation technique for determining partial molar enthalpies in mixtures of gases and liquids from single simulations, without relying on particle insertions, deletions, or identity changes. The method can also be applied to systems with chemical reactions. We demonstrate our method for binary mixtures of Weeks-Chandler-Anderson particles by comparing with conventional simulation techniques, as well as for a simple model that mimics a chemical reaction. The method considers small subsystems inside a large reservoir (i.e., the simulation box), and uses the construction of Hill to compute properties in the thermodynamic limit from small-scale fluctuations. Results obtained with the new method are in excellent agreement with those from previous methods. Especially for modeling chemical reactions, our method can be a valuable tool for determining reaction enthalpies directly from a single MD simulation. [ABSTRACT FROM AUTHOR]

The Monte Carlo (MC) and molecular dynamics (MD) methodologies are now well established for computing equilibrium properties in homogeneous fluids. This is not yet the case for the direct simulation of two-phase systems, which exhibit nonuniformity of the density distribution across the interface. We have performed direct MC and MD simulations of the liquid-gas interface of n-pentane using a standard force-field model. We obtained density and pressure components profiles along the direction normal to the interface that can be very different, depending on the truncation and long range correction strategies. We discuss the influence on predicted properties of different potential truncation schemes implemented in both MC and MD simulations. We show that the MD and MC profiles can be made in agreement by using a Lennard-Jones potential truncated via a polynomial function that makes the first and second derivatives of the potential continuous at the cutoff distance. In this case however, the predicted thermodynamic properties (phase envelope, surface tension) deviate from experiments, because of the changes made in the potential. A further readjustment of the potential parameters is needed if one wants to use this method. We conclude that a straightforward use of bulk phase force fields in MD simulations may lead to some physical inconsistencies when computing interfacial properties.© 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The adsorption of carbon monoxide and nitrogen molecules at the surface of four forms of solid water is investigated by means of grand canonical Monte Carlo simulations. The trapping ability of crystalline Ih and low-density amorphous ices, along with clathrate hydrates of structures I and II, is compared at temperatures relevant for astrophysics. It is shown that when considering a gas phase that contains mixtures of carbon monoxide and nitrogen, the trapping of carbon monoxide is favored with respect to nitrogen at the surface of all solids, irrespective of the temperature. The results of the calculations also indicate that some amounts of molecules can be incorporated in the bulk of the water structures, and the molecular selectivity of the incorporation process is investigated. Again, it is shown that incorporation of carbon monoxide is favored with respect to nitrogen in most of the situations considered here. In addition, the conclusions of the present simulations emphasize the importance of the strength of the interactions between the guest molecules and the water network. They indicate that the accuracy of the corresponding interaction potentials is a key point, especially for simulating clathrate selectivity. This highlights the necessity of having interaction potential models that are transferable to different water environments.