Possible mechanisms of increase in heat capacity of nanostructured metals

The problem of anomalously high experimental values of the heat capacity of metallic nanoclusters has been analyzed in terms of the thermodynamics of the surfaces, as well as based on the data of computer experiment. The heat capacity of ideal face-centered cubic (fcc) palladium clusters with a diameter of 6 nm in the temperature range of 150–300 K has been investigated using the molecular dynamics method with several tight-binding potentials. It has been found that, at a temperature $T$ = 150 K, the heat capacity of a Pd nanoparticle exceeds the heat capacity of the bulk material by 12–16%. Based on the results of the theoretical treatment, computer simulation, and analysis of experimental data, it has been concluded that an increase in the heat capacity of the compacted nanomaterial is not determined by the high heat capacity of individual clusters. Apparently, the significant increase in the heat capacity of compact nanomaterials can be explained either by their disordered state or by the high content of different types of impurities, mainly hydrogen.