Vibrational entropy of disorder in Cu3Au with different degrees of short-range order

Abstract

L1₂ ordered Cu₃Au and fcc-disordered samples with different degrees of short-range order were synthesised by annealing and/or quenching experiments. Low-temperature heat capacities were determined by relaxation calorimetry. From these data the vibrational entropy of disorder was derived. The calorimetric results show that the vibrational entropy does not depend on the degree of short-range order. The calorimetric investigations were complemented by density functional calculations with different functionals simulating various atomic configurations by super cells of different size. Using super cells containing 32 atoms, the computed entropies show only small variations with the change of short-range order in good agreement with the calorimetric results. Using, however, super cells with only 8 atoms, the results depend strongly on the chosen atomic configuration at variance with the calorimetric data. This result is important for investigating substances with larger molecules (e.g., silicate solid solutions) because such investigations are typically limited on super cells containing only a few sites on which substitution takes place.