Binary Clusters AuPt and Au₆Pt:  Structure and Reactivity within Density Functional Theory

Abstract

Within density functional theory with the general gradient approximation for the exchange and correlation, the bimetallic clusters AuPt and Au(6)Pt have been studied for their structure and reactivity. The bond strength of AuPt lies between those of Au(2) and Pt(2), and it is closer to that of Au(2). The Pt atom is the reactive center in both AuPt and AuPt(+) according to electronic structure analysis. AuPt(+) is more stable than AuPt. Au(6)Pt prefers electronic states with low multiplicity. The most stable conformation of Au(6)Pt is a singlet and has quasi-planar hexagonal frame with Pt lying at the hexagonal center. The doping of Pt in Au cluster enhances the chemical regioselectivity of the Au cluster. The Pt atom essentially serves as electron donor and the Au atoms bonded to the Pt atom acts as electron acceptor in Au(6)Pt. The lowest triplet of edge-capped rhombus Au(6)Pt clusters is readily accessible with very small singlet-triplet energy gap (0.32 eV). O(2) prefers to adsorb on Au and CO prefers to adsorb on Pt. O(2) and CO have stronger adsorption on AuPt than they do on Au(6)Pt. CO has a much stronger adsorption on AuPt bimetallic cluster than O(2) does. The adsorption of CO on Pt modifies the geometry of AuPt bimetallic clusters.

Structural, electronic and magnetic properties of small gold clusters with a copper impurity

“…This situation can be understood in terms of the similar atomic configurations and good structure compatibility between Au and Cu. The maintenance of planar structures was also observed in previous work [24,25],…”

Thermal NH Bond Activation on Anionic and Cationic Platinum Clusters: Non‐Predetermined Reaction Pathways Indicate Transitions to a Bulk Surface Reactivity

“…[58][59][60][61][62] This functional was also used in previous studies of related systems. [19,63,64] The Pt 2 dissociation energy at the DFT/BPW91 level was calculated as 3.44 eV, which is in good agreement with a full-relativistic DFT calculation result of 3.12-3.33 eV. [65] As to the basis set, the Stuttgart ECP60MWB pseudopotential together with the corresponding basis set developed by Dolg, Andrae and Martin [66][67][68] was placed on the Pt atoms, where 60 stands for the number of core electrons.…”

Methyloxy Substituted Heteroleptic Bis(phthalocyaninato) Yttrium Complexes: Density Functional Calculations

“…[19,20] The LANL2DZ basis set is the most efficient and widely used among all the basis sets in the Gaussian 03 program suite. [6,17,21,22] The Berny algorithm using redundant internal coordinates was employed in energy minimization, and the default cutoffs were used throughout. [30] The C 4 symmetry of 1 and C 4v symmetry of 2 and 3 were detected in the input structures and then enforced by the program.…”

“…[6,17,21,22] However, only complexes of yttrium are selected for the present study due to the lack of an appropriate basis set to study compounds of rare earth metals with complicated f electrons. The hybrid functional PBE0, [23a,b] which is based on the Perdew-Burke-Erzenrhof (PBE) generalized gradient functional [23c] with 25 % of exact exchange, has been reported to give more accurate results than B3LYP and has gained a wide range of applications.…”