Impurity effects on solid–solid transitions in atomic clusters

Abstract

We use the harmonic superposition approach to examine how a single atom substitution affects low-temperature anomalies in the vibrational heat capacity (C_V) of model nanoclusters. Each anomaly is linked to competing solidlike “phases”, where crossover of the corresponding free energies defines a solid–solid transition temperature (T_s). For selected Lennard-Jones clusters we show that T_s and the corresponding C_V peak can be tuned over a wide range by varying the relative atomic size and binding strength of the impurity, but excessive atom-size mismatch can destroy a transition and may produce another. In some tunable cases we find up to two additional C_V peaks emerging below T_s, signalling one- or two-step delocalisation of the impurity within the ground-state geometry. Results for Ni₇₄X and Au₅₄X clusters (X = Au, Ag, Al, Cu, Ni, Pd, Pt, Pb), modelled by the many-body Gupta potential, further corroborate the possibility of tuning, engineering, and suppressing finite-system analogues of a solid–solid transition in nanoalloys.