In this work, a first-principles systematic study of (Pt3Cu)n, n = 1–9, clusters was performed employing the linear combination of Gaussian-type orbital auxiliary density functional theory approach. The growth of the clusters has been achieved by increasing the previous cluster by one Pt3Cu unit at a time. To explore in detail the potential energy surface of these clusters, initial structures were obtained from Born–Oppenheimer molecular dynamics trajectories generated at different temperatures and spin multiplicities. For each cluster size, several dozens of structures were optimized without any constraints. The most stable structures were characterized by frequency analysis calculations. This study demonstrates that the obtained most stable structures prefer low spin multiplicities. To gain insight into the growing pattern of these systems, average bond lengths were calculated for the lowest stable structures. This work reveals that the Cu atoms prefer to be together and to localize inside the cluster structures. Moreover, these systems tend to form octahedra moieties in the size range of n going from 4 to 9 Pt3Cu units. Magnetic moment per atom and spin density plots were obtained for the neutral, cationic, and anionic ground state structures. Dissociation energies, ionization potential, and electron affinity were calculated, too. The dissociation energy and the electron affinity increase as the number of Pt3Cu units grows, whereas the ionization potential decreases.

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Elucidation of the chemical reactivity of metal clusters is often cumbersome due to the nonintuitive structures of the corresponding transition states. In this work, a hierarchical transition-state algorithm as implemented in the deMon2k code has been applied to locate transition states of small sodium clusters with 6–10 atoms. This algorithm combines the so-called double-ended interpolation method with the uphill trust region method. The minimum structures needed as input were obtained from Born–Oppenheimer molecular dynamics simulations. To connect the found transition states with the corresponding minimum structures, the intrinsic reaction coordinates were calculated. This work demonstrates how nonintuitive rearrangement mechanisms can be studied in metal clusters.

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