On the Electronic Structure of Organometallic Palladium Clusters of Medium and Large Size: A Theoretical Study

Abstract

International audienceBased on density functional calculations on model systems, the electronic structure of medium and large ligated palladium clusters is discussed herein. Among all the studied clusters, the electronic structure of Pd30(CO)26(PR3)10 , Pd69(CO)36(PR3)18 and Pd145(CO)56(PR3)30 clusters is analyzed in details. It is shown that the evolution of the band gap can be correlated to the average Pd-Pd bond length rather than n, the nuclearity of the cluster

Elucidating the Electronic Structure of the Ligated Cuboctahedral Palladium Cluster [Pd13(μ4-C7H7)6]2+

“…Over the last decades, it became apparent that palladium in its zero-valent state, forms unique highly condensed nano-sized carbonyl-ligated clusters [2,3], distinguishing itself from other elements, including the other two Group 10 congeneric Ni and Pt metals [4][5][6] Indeed, relatively weak metal-metal and metal-carbonyl (and/or phosphine) connectivity must be responsible for the rich variety of structural arrangements reported for these high-nuclearity ligated clusters, which can extend up to 165 atoms (so far) [7]. A substantial number of them have been crystallographically identified [3], and theoretically investigated [8][9][10]. Interestingly, they adopt various shapes, ranging from ''bulk-like'' cubic closed packed and/or hexagonal closed packed architectures to, also compact but "molecular" icosahedral shapes.…”

Size-dependent properties of transition metal clusters: from molecules to crystals and surfaces – computational studies with the program ParaGauss

“…3,45,60 The intrinsic properties of nearly spherical TM clusters of size n (or effective radius r p n 1/3 ) scale as a power series in terms of the surface-tovolume ratio r À1 p n À1/3 ; analogous relations hold for lower dimensional structures. 43,44,46,51,61 In summary, a cluster scaling procedure can be described in general as follows. 14 Yet, also nonlinear cluster scaling extrapolations have been carried out.…”

“…45 Note that any other quantity linear in n À1/3 may serve equally well as the independent variable in a cluster scaling study; common examples are the average bond length d av or the average coordination number CN av . 43,44,46,51,61 In summary, a cluster scaling procedure can be described in general as follows. The values of the property of interest are calculated for a series of model clusters (Section 2.2) of sizes {n i }.…”