Small Pd clusters: A comparison of phenomenological and<i>ab initio</i>approaches

Rogan, José; García, Gabriela; Valdivia, J. A.; Orellana, Walter; Romero, Aldo H.; Ramírez, Raúl Madrid; Kiwi, Miguel

doi:10.1103/physrevb.72.115421

Cited by 64 publications

(68 citation statements)

References 37 publications

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“…The competitive isomer for Pd 14 also has a distorted hexagonal bilayer (HBL) structure, but with lower symmetry (C 1 ) and a relative energy of 0.09 eV. The global minimum of Pd 13 reported here is found to be different from the compact icosahedron structure predicted as the GM in references [67][68][69].…”

Section: Pd Clustersmentioning

confidence: 58%

Application of a parallel genetic algorithm to the global optimization of medium-sized Au–Pd sub-nanometre clusters

2018

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Abstract. To contribute to the discussion of the high activity and reactivity of Au-Pd system, we have adopted the BPGA-DFT approach to study the structural and energetic properties of medium-sized AuPd sub-nanometre clusters with 11-18 atoms. We have examined the structural behaviour and stability as a function of cluster size and composition. The study suggests 2D-3D crossover points for pure Au clusters at 14 and 16 atoms, whereas pure Pd clusters are all found to be 3D. For Au-Pd nanoalloys, the role of cluster size and the influence of doping were found to be extensive and non-monotonic in altering cluster structures. Various stability criteria (e.g. binding energies, second differences in energy, and mixing energies) are used to evaluate the energetics, structures, and tendency of segregation in sub-nanometre Au-Pd clusters. HOMO-LUMO gaps were calculated to give additional information on cluster stability and a systematic homotop search was used to evaluate the energies of the generated global minima of monosubstituted clusters and the preferred doping sites, as well as confirming the validity of the BPGA-DFT approach.

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Section: Pd Clustersmentioning

confidence: 58%

Application of a parallel genetic algorithm to the global optimization of medium-sized Au–Pd sub-nanometre clusters

2018

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“…[38] Note that at this level, it is difficult to determine the ground state of Pd 5 because the relative energy ordering of electronic states differs substantially from one level of theory to an-other. A large scale of CASSCF and MRSDCI calculations on electronic states of Pd 5 reveal that there are several lowlying electronic states of different geometries for Pd 5 . [39] B3LYP calculations for Pd 6 show a distorted octahedron ground state with a D 4h symmetry.…”

Section: Resultsmentioning

confidence: 99%

“…If a large number of theoretical papers are already devoted to the study of these compounds, they generally focus on the determination of the geometry of the ground state. To this end, palladium clusters have been simulated by a wide range of methods, ranging from "simple" semi-empirical methods, [4,5] to the most complex post-SCF methods, [6,7] as well as density functional theory (DFT). [8][9][10][11][12] Recently, palladium clusters with larger nuclearity were also studied by molecular dynamics.…”

Section: Introductionmentioning

confidence: 99%

DFT Study of Small Palladium Clusters Pd_n and Their Interaction with a CO Ligand (n = 1–9)

Zanti

Peeters

2009

Eur J Inorg Chem

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This paper presents a theoretical study of palladium clusters Pd n of low nuclearity, ranging from 1 to 9, completed by their interactions with a carbonyl ligand (Pd n CO). The simulations were performed at the DFT (B3LYP-Lanl2DZ) level. Small palladium clusters are deltahedral structures characterized by a triplet ground state (Pd 2 to Pd 7 ) or a quintet ground state for larger nuclearities (Pd 8 and Pd 9 ). Various electronic states relatively close in energy are present. These states have close geometries but differ by their electron density distribution. A significant electronic population of the 5s orbital is needed to explain the existence and cohesion of palladium-palladium bonds. These latter are formed by the combination of sd hybrid orbitals and get stronger as the 5s character increases. The relative stability of palladium clusters increases with their nuclearity and the study of fragmentation reactions

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“…4 The Pd 9 cluster The Pd 9 cluster has already been studied in the gas phase [28][29][30] as well as on a MgO support [11]. To the best of our knowledge, Pd clusters on thin metal supported MgO films have not been considered yet.…”

Section: Methodsmentioning

confidence: 98%

How to observe the oxidation of magnesia‐supported Pd clusters by scanning tunnelling microscopy

Walter

Moseler

2010

Physica Status Solidi (b)

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The structure of adsorbed bare and oxidised Pd-9 clusters on a MgO(001) bilayer supported by an Ag(001) surface are studied by density functional theory (DFT). Results for the bare cluster are compared with corresponding calculations of Pd9 on a free-standing MgO(001) trilayer - a system that already reproduces the adsorption properties of thick MgO films. A 3D double trigonal antiprism is compared to a 2D fragment of a Pd(111) plane. In contrast to the findings for gold clusters, the Pd-9 3D ground state on a thick MgO film is still energetically favourable on a thin metal supported MgO film - despite the substantial charge transfer from the metal support to the 2D cluster. Simulated scanning tunnelling microscopy images predict that the oxide formation should be easily detectable for negative bias voltages, since the highest occupied molecular orbitals of both the pristine as well as the oxidised clusters possess a strong Pd(d) contribution localised on the Pd atoms. At positive bias, the nodal structure of delocalised unoccupied orbitals sometimes masks the nuclear positions. [GRAPHICS

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Small Pd clusters: A comparison of phenomenological andab initioapproaches

Cited by 64 publications

References 37 publications

Application of a parallel genetic algorithm to the global optimization of medium-sized Au–Pd sub-nanometre clusters

Application of a parallel genetic algorithm to the global optimization of medium-sized Au–Pd sub-nanometre clusters

DFT Study of Small Palladium Clusters Pd_n and Their Interaction with a CO Ligand (n = 1–9)

How to observe the oxidation of magnesia‐supported Pd clusters by scanning tunnelling microscopy

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Small Pd clusters: A comparison of phenomenological andab initioapproaches

Cited by 64 publications

References 37 publications

Application of a parallel genetic algorithm to the global optimization of medium-sized Au–Pd sub-nanometre clusters

Application of a parallel genetic algorithm to the global optimization of medium-sized Au–Pd sub-nanometre clusters

DFT Study of Small Palladium Clusters Pdn and Their Interaction with a CO Ligand (n = 1–9)

How to observe the oxidation of magnesia‐supported Pd clusters by scanning tunnelling microscopy

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DFT Study of Small Palladium Clusters Pd_n and Their Interaction with a CO Ligand (n = 1–9)