Statistical Mechanics of Nanoscale Metallic Materials Based on Thermodynamic Availability

When characterizing the equilibrium behavior of small metallic systems, capillary effects can strongly influence the thermal behavior and need to be taken into account in a complete thermodynamic analysis. Although a variety of approaches have been offered to incorporate these effects, they sometimes invoke certain intensive thermodynamic quantities (e.g., chemical potentials) that are not well-defined when dealing with a physically and/or chemically inhomogeneous interfacial region.It has been proposed that many of these difficulties can be resolved by employing the thermodynamic availability function rather than the conventional free energy potentials [R.C. Cammarata, Phil Mag. 88, 927 (2008); R.C. Cammarata, Sol. State Phys. 61, 1 (2009)]. When applied to statistical mechanical calculations, capillary effects on nanoscale system behavior can be obtained in a natural and rigorous way. This procedure will be briefly reviewed and then applied to nanoscale metallic fluid and solid systems. Important issues contrasting the thermodynamic differences between fluid and solid surfaces and how they need to be included in order to obtain physically meaningful results will be discussed. Applications to gas adsorption and nucleation will be presented.