Metal clusters with hidden ground states: Melting and structural transitions in Al115(+), Al116(+), and Al117(+).

Heat capacities measured as a function of temperature for Al(115)(+), Al(116)(+), and Al(117)(+) show two well-resolved peaks, at around 450 and 600 K. After being annealed to 523 K (a temperature between the two peaks) or to 773 K (well above both peaks), the high temperature peak remains unchanged but the low temperature peak disappears. After considering the possible explanations, the low temperature peak is attributed to a structural transition and the high temperature peak to the melting of the higher enthalpy structure generated by the structural transition. The annealing results show that the liquid clusters freeze exclusively into the higher enthalpy structure and that the lower enthalpy structure is not accessible from the higher enthalpy one on the timescale of the experiments. We suggest that the low enthalpy structure observed before annealing results from epitaxy, where the smaller clusters act as a nucleus and follow a growth pattern that provides access to the low enthalpy structure. The solid-to-solid transition that leads to the low temperature peak in the heat capacity does not occur under equilibrium but requires a superheated solid.