First Principles Study of Ga₍₂₀₋x₎Alx⁺ Nanoalloys: Structure, Thermodynamics and Phase Diagram

Nanoalloys (a finite framework of two or more metal atoms) represent a rapidly growing field owing to the possibilities of tuning its properties as desired for various applications. Their properties are size, shape, composition, chemical ordering, and temperature dependent, thereby offering a large playground for varied research motivations. This thesis documents the investigations on how the addition of aluminium affects the cationic gallium clusters, both in terms of geometric & electronic structure and thermodynamics, which have been observed to show greater-than-bulk melting behaviour for small sizes. A specific cluster size of 20 atoms is selected, Ga₍₂₀₋x₎Alx⁺, with the overall intention of creating a phase diagram which is the most reliable way to predict the phase changes in the system. All the first principles (density functional theory) based Born-Oppenheimer molecular dynamics calculations have been performed in the microcanonical ensemble. Melting behaviour is first studied in the pure Al₂₀⁺ clusters and then in three representative clusters of Ga₍₂₀₋x₎Alx⁺ series: Ga₁₉Al⁺, Ga₁₁Al₉⁺ and Ga₃Al₁₇⁺ clusters. We observe that all the three nanoalloy compositions show greater-than-bulk melting behaviour behaviour as well and in Ga₁₉Al⁺, specifically, Al prefers the internal sites, contrary to the previous arguments. We go on to complete the solid-liquid-like melting phase diagram using the calculated information and further propose a model of these greater-than-bulk melting clusters to be components of the corresponding bulk phases, whether metals or alloys, with additional size-dependent contributions added to it.