Estimating metastable thermodynamic properties by isochoric extrapolation from stable states.

The description of metastable fluids, those in local but not global equilibrium, remains an important problem of thermodynamics, and it is crucial for many industrial applications and all first order phase transitions. One way to estimate their properties is by extrapolation from nearby stable states. This is often done isothermally, in terms of a virial expansion for gases or a Taylor expansion in density for liquids.

Free energy of critical droplets-from the binodal to the spinodal.

Arguably, the main challenge of nucleation theory is to accurately evaluate the work of formation of a critical embryo in the new phase, which governs the nucleation rate. In Classical Nucleation Theory (CNT), this work of formation is estimated using the capillarity approximation, which relies on the value of the planar surface tension. This approximation has been blamed for the large discrepancies between predictions from CNT and experiments.

Classical density functional theory for interfacial properties of hydrogen, helium, deuterium, neon, and their mixtures.

We present a classical density functional theory (DFT) for fluid mixtures that is based on a third-order thermodynamic perturbation theory of Feynman-Hibbs-corrected Mie potentials. The DFT is developed to study the interfacial properties of hydrogen, helium, neon, deuterium, and their mixtures, i.e.

Equation of state for confined fluids.

Fluids confined in small volumes behave differently than fluids in bulk systems. For bulk systems, a compact summary of the system's thermodynamic properties is provided by equations of state. However, there is currently a lack of successful methods to predict the thermodynamic properties of confined fluids by use of equations of state, since their thermodynamic state depends on additional parameters introduced by the enclosing surface.

Perturbation theories for fluids with short-ranged attractive forces: A case study of the Lennard-Jones spline fluid.

It is generally not straightforward to apply molecular-thermodynamic theories to fluids with short-ranged attractive forces between their constituent molecules (or particles). This especially applies to perturbation theories, which, for short-ranged attractive fluids, typically must be extended to high order or may not converge at all. Here, we show that a recent first-order perturbation theory, the uv-theory, holds promise for describing such fluids.

Choice of reference, influence of non-additivity, and present challenges in thermodynamic perturbation theory for mixtures.

This work revisits the fundamentals of thermodynamic perturbation theory for fluid mixtures. The choice of reference and governing assumptions can profoundly influence the accuracy of the perturbation theory. The statistical associating fluid theory for variable range interactions of the generic Mie form equation of state is used as a basis to evaluate three choices of hard-sphere reference fluids: single component, additive mixture, and non-additive mixture.

Equation of state and force fields for Feynman-Hibbs-corrected Mie fluids. II. Application to mixtures of helium, neon, hydrogen, and deuterium.

We extend the statistical associating fluid theory of quantum corrected Mie potentials (SAFT-VRQ Mie), previously developed for pure fluids [Aasen et al., J. Chem.