Transition and noble metal clusters have proven to be critical novel materials, potentially offering major advantages over conventional catalysts in a range of value-added catalytic processess such as carbon dioxide transformation to methanol. In this work, a systematic computational study of CO2 adsorption on gas-phase Cu4-xPtx (x = 0-4) clusters is performed. An exhaustive potential energy surface exploration is initially performed using our recent density functional theory basin-hopping global optimization implementation. Ground-state and low-lying energy isomers are identified for Cu4-xPtx clusters. Secondly, a CO2 molecule adsorption process is analyzed on the ground-state Cu4-xPtx configurations, as a function of cluster composition. Our results show that the gas-phase linear CO2 molecule is deformed upon adsorption, with its bend angle varying from about 132° to 139°. Cu4-xPtx cluster geometries remain unchanged after CO2 adsorption, with the exception of Cu3Pt1 and Pt4 clusters. For these particular cases, a structural conversion between the ground-state geometry and the corresponding first isomer configurations is found to be assisted by the CO2 adsorption. For all clusters, the energy barriers between the ground-state and first isomer structures are explored. Our calculated CO2 adsorption energies are found to be larger for Pt-rich clusters, exhibiting a volcano-type plot. The overall effect of a hybrid functional including dispersion forces is also discussed.

The threshold method is used to explore the potential energy surface of the Pt(1)Pd(12) bimetallic cluster, defined by the Gupta semiempirical potential. A set of helical structures, which follow a Bernal tetrahelix pattern, correspond to local minima for the Pt(1)Pd(12) cluster, characterizing the region of the energy landscape where these structures are present. Both right-handed and left-handed chiral forms were discovered in our searches. Energetic and structural details of each of the tetrahelices are reported as well as the corresponding transition probabilities between these structures and with respect to the icosahedron-shaped global minimum structure via a disconnectivity graph analysis.

We present a systematic study of the structural changes of 19-atom Pd n Pt 19-n nanoparticles as a function of composition, modeling the interatomic interactions with the many-body Gupta potential and using a genetic algorithm to obtain the lowest energy structures for all possible compositions. Topological analysis reveals that most of the structures are based on icosahedral packings and are strongly composition dependent. The pure Pd 19 nanoparticle exhibits a double icosahedral geometry, while the Ino decahedron is the basis of the Pt 19 cluster structure, which has a lower symmetry. Several structural motifs of the predicted lowest energy configurations are observed for bimetallic clusters in the range of compositions studied here. Six ideal structural families have been identified. Our results show that, for Pt-rich clusters, Pt atoms segregate into the core and the number of Pd-Pt bonds increases, while for Pd-rich clusters, the surface-segregated Pd atoms tend not to be nearest-neighbors. X-ray diffraction structure factors are simulated for all the predicted structures.

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