https://doi.org/10.1140/epjd/e2008-00175-2
Free energies of ionic nanoclusters. Solid and coexistent solid-liquid states
Centre of Molecular Sciences and Materials, Department of Chemistry
and Biochemistry, Faculty of Sciences, University of Lisboa Campo
Grande, Bloco C8, 1749-016 Lisboa, Portugal
Corresponding author: a fsilva@fc.ul.pt
Received:
16
July
2008
Published online:
3
October
2008
A strategy to overcome some specific problems associated to the computation of free energies in clusters is presented. Free energies and entropies of solid KCl nanoclusters are determined by thermodynamic integration, and Watanabe and Reinhardt's dynamical method, based on molecular dynamics simulations. The values are in good agreement with experimental data. From a previous theoretical prediction of the caloric curve, T(E), for the coexistence region, an equation is derived to compute the free energies of the clusters at the solid-liquid coexistence. The results are discussed in the context of the thermodynamic stability of phase coexistent states for finite and infinite systems, yielding consistent conclusions.
PACS: 61.46.-w – Structure of nanoscale materials / 64.70.Nd – Structural transitions in nanoscale materials
© EDP Sciences, Società Italiana di Fisica, Springer-Verlag, 2008
