Solid-solid transitions in Pd-Pt nanoalloys

Solid-solid transformations in Pd-Pt nanoalloys in the size range 32-38 atoms and for different compositions are computationally studied by the superposition approximation to the partition function, and by molecular dynamics simulations. A broad spectrum of transition types is shown to take place. These transition types are: (i) one-to-one type, in which the global minimum, which is dominant at low temperatures, transforms into another single isomer with increasing temperature; (ii) one-to-many type, in which the transition is from a single isomer to a family of other isomers; (iii) many-to-many type, in which the transition is between two different families of isomers; (iv) many-to-one type, in which the effect of vibrational entropy is to greatly reduce the number of relevant structures with increasing temperatures. We provide a rationale for these behaviors, which stem from the interplay between energetics and vibrational entropy effects. The vibrational entropy is explained by analyzing the vibrational density of states and the specific features of the normal modes. Quantum effects on the structural transitions are also discussed.