Theory of the structural fluctuation of Au55 clusters

Stabilities and structural fluctuations of both neutral and charged Au₅₅ clusters are examined and discussed in relation to recent experimental observations of small gold particles with an electron microscope. Transition probabilities between the icosahedral and cuboctahedral structures are calculated according to the transition state theory using a model potential consisting of attractive many-body, repulsive pairwise and Coulomb parts. It is shown that for a neutral cluster the cuboctahedral structure has too short life time to be observed around room temperature and that, on the other hand, for more than 6-fold multiply charged clusters, both structures have life times of the order of 0.1 s around room temperature and, therefore, the transition between them can be observed.     

Naked Au55 clusters: dramatic effect of a thiol-terminated dendrimer

Reaction of the thiol-terminated fourth-generation dendrimer 2-G4 (96 SH groups) with the gold cluster compound Au55(PPh3)12Cl6 in a 3:1 molar ratio in dichloromethane results in the formation of bare Au55 clusters. The cuboctahedrally shaped Au55 particles coalesce to well-formed microcrystals (Au55) infinity. The role of the dendrimer is not only to remove the phosphine and chlorine ligands but also to act as an ideal matrix for perfect crystal growth. Transmission electron microscopy (TEM), small- and wide-angle X-ray diffraction (SAXRD and WAXRD) measurements indicate a structure where rows of edge-linked Au55 building blocks form a distorted cubic lattice. The X-ray data fit best if a 5% reduction of the Au-Au bond length in the Au55 clusters is assumed, in agreement with previous extended X-ray absorption fine structure (EXAFS) measurements. Energy-dispersive X-ray spectroscopy (EDX) analyses and IR investigations show the absence of PPh3 and Cl in the microcrystals.     

Structural fluctuation and atom-permutation in transition-metal clusters

The atomic structure and thermodynamic properties of transition-metal clusters containingN atoms are investigated forN=6 and 7 using the method of molecular dynamics, where Gupta's potential taking into account many-body interaction is employed. The caloric curve (total energy — temperature curve) and the structural fluctuations are studied. The “fluctuating state” is found forN=6 in the region of the temperature near below the melting point, where clusters undergo structural transition from one isomer to others without making any topological change. The fluctuating state differs from the coexistence state in that the former involves no atomic diffusion, and goes to a structural phase transition of the bulk whenN is increased. On the other hand, the motion of atom-permutation is found in the low-temperature region of the liquid state, being induced by the cooperative motion of two atoms. It is discussed that such a motion easily occurs along the surface and may be considered to be one of the characteristics of small clusters. The fluctuating state is discussed in relation to the structural fluctuation of gold clusters observed experimentally.     

Optical plasmon losses in stabilized Au55 clusters

Au₅₅ cluster compounds are investigated by optical spectroscopy and TEM. The optical spectra appear to be rather structureless, neither showing a collective excitation resonance nor exhibiting distinct absorption bands known from lower nuclearity clusters. We discuss changes of the electronic properties compared to larger Au clusters affecting both, 6sp electrons and5d-6sp interband transitions, the cluster-ligand-interaction being considered as a charge transfer process. We additionally report on a low temperature instability of the cluster compound, which results in changed optical extinction spectra. A characteristic absorption feature at λ=400 nm is attributed to small, ligand-free Au cluster fragments.     

The relevance of shape and size of Au55 clusters

This critical review deals with the history of Au(55)(PPh(3))(12)Cl(6) and its derivatives from the very beginning in 1981 to date. Au(55) clusters obtain their special interest from their ultimate size and their ideal cuboctahedral structure. They are part of the family of so-called full-shell clusters, particles with perfectly completed geometries, also represented by icosahedral Au(13) clusters. Bare as well as ligand protected Au(55) clusters not only exhibit special chemical and physical stability, but draw their attention particularly from their unique electronic properties. Single electron switching at room temperature becomes possible, giving rise for development of applications in future nanoelectronic devices. A predominantly size-determined property of the 1.4 nm particles becomes obvious with respect of biological response. Au(55) clusters indicate an unusual cytotoxicity which seems to be caused by the unusually strong interaction between the 1.4 nm particles and the major grooves of DNA. Only marginally smaller or larger particles show drastically reduced toxicity, whereas significantly larger gold nanoparticles are completely non-toxic. Both, the electronic perspectives as well as the relevance in toxicology are at very early stages of development (75 references).     

Chromatographic isolation of "missing" Au55 clusters protected by alkanethiolates

We report on the first synthesis of alkanethiolate-protected Au55 (11 kDa), which has been a "missing" counterpart of Schmid's Au55(PR3)12Cl6. Au:SCx clusters (x = 12, 18) were prepared by the reaction of alkanethiol (CxSH) with polymer-stabilized Au clusters ( approximately 1.3 nm) and subsequently incubated in neat CxSH. The resulting clusters were successfully fractionated by recycling gel permeation chromatography into Au approximately 38:SCx and Au approximately 55:SCx and identified by laser-desorption ionization mass spectrometry. The Au approximately 55:SCx clusters exhibited structured optical spectra, suggesting molecular-like properties. The thiolate monolayers were found to be liquid-like on the basis of the IR spectrum and the monolayer thickness, which was estimated from the hydrodynamic diameter.     

Structural and thermodynamic properties of Au2�C20 clusters

Isolated neutral gold clusters with 2?C20 atoms are studied theoretically using a parametrized density-functional tight-binding method combined with genetic algorithms. The structural and energetic properties are analyzed by studying the total energy per atom, the relative stability, the overall shape, and through a common-neighbor analysis. In addition, the temperature dependence of the vibrational heat capacities of the optimized gold clusters has been studied for the first time. We find the vibrational heat capacity of the clusters to be strongly size dependent at low temperature. For instance, the cluster with 6 atoms has a high vibrational heat capacity at low temperature, a finding rationalized in terms of structure.     

Melting phenomena: effect of composition for 55-atom Ag-Pd bimetallic clusters

Understanding the composition effect on the melting processes of bimetallic clusters is important for their applications. Here, we report the relationship between the melting point and the metal composition for the 55-atom icosahedral Ag-Pd bimetallic clusters by canonical Monte Carlo simulations, using the second-moment approximation of the tight-binding potentials (TB-SMA) for the metal-metal interactions. Abnormal melting phenomena for the systems of interest are found. Our simulation results reveal that the dependence of the melting point on the composition is not a monotonic change, but experiences three different stages. The melting temperatures of the Ag-Pd bimetallic clusters increase monotonically with the concentration of the Ag atoms first. Then, they reach a plateau presenting almost a constant value. Finally, they decrease sharply at a specific composition. The main reason for this change can be explained in terms of the relative stability of the Ag-Pd bimetallic clusters at different compositions. The results suggest that the more stable the cluster, the higher the melting point for the 55-atom icosahedral Ag-Pd bimetallic clusters at different compositions.     

Geometrical structures of trimetallic Ag–Pd–Pt and Au–Pd–Pt clusters up to 147 atoms

Structural Chemistry - The core-shell morphologies of (PdPt)coreAgshell and (PdPt)coreAushell up to 147 atoms are investigated. The structural optimization of M–Pd–Pt (M = Ag or Au) is...     

CO oxidation on unsupported Au55, Ag55, and Au25Ag30 nanoclusters

Using density functional calculations, we demonstrate a catalytic reaction path with activation barriers of less than 0.5 eV for CO oxidation on the neutral and unsupported icosahedral nanoclusters of Au(55), Ag(55), and Au(25)Ag(30). Both CO and O(2) adsorb more strongly on these clusters than on the corresponding bulk surfaces. The reaction path consists of an intermediate involving OOCO complex through which the coadsorption energy of CO and O(2) on these clusters is expected to play an important role in the reaction. Based on the studies for the Au and Ag nanoclusters, a model alloy nanocluster of Au(25)Ag(30) was designed to provide a larger coadsorption energy for CO and O(2) and was anticipated to be a better catalyst for CO oxidation from energetic analysis.     

Large-scale synthesis of thiolated Au25 clusters via ligand exchange reactions of phosphine-stabilized Au11 clusters

Phosphine-stabilized Au11 clusters in chloroform were reacted with glutathione (GSH) in water under a nitrogen atmosphere. The resulting Au:SG clusters exhibit an optical absorption spectrum similar to that of Au25(SG)18, which was isolated as one of the major products from chemically prepared Au:SG clusters (Negishi, Y. et al. J. Am. Chem. Soc. 2005, 127, 5261). Rigorous characterization by optical spectroscopy, electrospray ionization mass spectrometry, and polyacrylamide gel electrophoresis confirms that the Au25(SG)18 clusters were selectively obtained on the sub-100 mg scale by ligand exchange reaction under aerobic conditions. The ligand exchange strategy offers a practical and convenient method of synthesizing thiolated Au25 clusters on a large scale.     

Bidimensionality of 8-atom clusters of Au: first principles study and comparison with Ag clusters

We have calculated the lowest energy structures of 8-atom neutral gold clusters using the density functional theory approach. In contrast with current literature that finds kinetic energy to be the determinant component, we have found that the 2D structure is energetically favored due to a higher electron delocalization that stems from the relativistic contraction of Au atom size which cause 3D clusters to deform. This higher delocalization lowers the total energy of the 2D structures against the 3D ones. Silver clusters do not suffer this size contraction, hence there is no higher delocalization in the 2D clusters, and their fundamental structure will be 3D.     

Synthesis and stability of monolayer-protected Au38 clusters

A synthesis strategy to obtain monodisperse hexanethiolate-protected Au38 clusters based on their resistance to etching upon exposure to a hyperexcess of thiol is reported. The reduction time in the standard Brust-Schiffrin two-phase synthesis was optimized such that Au38 were the only clusters that were fully passivated by the thiol monolayer which leaves larger particles vulnerable to etching by excess thiol. The isolated Au38 was characterized by mass spectrometry, thermogravimetric analysis, optical spectroscopy, and electrochemical techniques giving Au38(SC6)22 as the molecular formula for the cluster. These ultrasmall Au clusters behave analogously to molecules with a wide energy gap between occupied (HOMO) and unoccupied levels (LUMO) and undergo single-electron charging at room temperature in electrochemical experiments. Electrochemistry provides an elegant means to study the electronic structure and the chemical stability of the clusters at different charge states. We used cyclic voltammetry and scanning electrochemical microscopy to unequivocally demonstrate that Au38 can be reversibly oxidized to charge states z = +1 or +2; however, reduction to z = -1 leads to desorption of the protecting thiolate monolayer. Although this reductive desorption of thiol from the cluster surface is superficially analogous to electrochemical desorption of planar self-assembled monolayers (SAMs) from macroscopic electrodes, the molecular details of the process are likely to be complicated based on the current view that the thiolate monolayer in clusters is in fact composed of polymeric Au-S complexes.     

Adsorption of O2 on tubelike Au24 and Au24- clusters

The nondissociative adsorptions of O(2) on the neutral and anionic Au(24) have been studied using the density functional theory (DFT) in the generalized gradient approximation. Their geometrical structures are optimized by using a combination of the relativistic effective core potential and all-electron potential with scalar relativistic corrections. It is found that the adsorptions of O(2) on the tubelike Au(24) and Au(24) (-) are more stable than it on their space-filled counterparts. Mulliken population analysis shows that the O(2) adsorbed on the tubelike Au(24) and Au(24) (-) got more electrons than on the amorphous ones, which may be a reason why the O(2) can be adsorbed more easily on the former rather than on the latter. Compared with the previous DFT studies of O(2) adsorbed on small Au(n) (n< or =10) clusters, we have shown that the O(2) can also be adsorbed on the neutral even Au(24) with an adsorption energy compatible with that on the small neutral odd gold clusters, but the adsorption energy of O(2) on the anionic Au(24) (-) is lower than that on the small anionic Au(n) with even n. In all the optimized geometrical structures of the O(2)-adsorbed Au(24) and Au(24) (-) clusters, including both tubelike and amorphous ones, we found that O(2) prefers its two O atoms to be attached to two near gold atoms with the least coordination number rather than only one O atom to be attached to one gold atom.     

Structural prediction of thiolate-protected Au38: a face-fused bi-icosahedral Au core

The lowest-energy structure of thiolate-group-protected Au38(SR)24 is with ab initio computations. A unique bi-isocahedral Au23 core is predicted for the Au38(SR)24 cluster, consistent with recent experimental and theoretical confirmation of the icosahedral Au13 core for the [Au25(SR)18]- cluster. The computed optical absorption spectrum and X-ray diffraction pattern are in good agreement with experimental measurements. Like the "magic-number" cluster [Au25(SR)18]-, the high stability and selectivity of the magic-number Au38(SR)24 cluster is attributed to high structural compatibility between the bi-isocahedral Au23 core and the 18 exterior staple motifs.     

Facile syntheses of monodisperse ultrasmall Au clusters

During our effort to synthesize the tetrahedral Au20 cluster, we found a facile synthetic route to prepare monodisperse suspensions of ultrasmall Au clusters AuN (N < 12) using diphosphine ligands. In our monophasic and single-pot synthesis, a Au precursor ClAu(I)PPh3 (Ph = phenyl) and a bidentate phosphine ligand P(Ph)2(CH2)(M)P(Ph)2 are dissolved in an organic solvent. Au(I) is reduced slowly by a borane-tert-butylamine complex to form Au clusters coordinated by the diphosphine ligand. The Au clusters are characterized by both high-resolution mass spectrometry and UV-vis absorption spectroscopy. We found that the mean cluster size obtained depends on the chain length M of the ligand. In particular, a single monodispersed Au11 cluster is obtained with the P(Ph)2(CH2)3P(Ph)2 ligand, whereas P(Ph)2(CH2)(M)P(Ph)2 ligands with M = 5 and 6 yield Au10 and Au8 clusters. The simplicity of our synthetic method makes it suitable for large-scale production of nearly monodisperse ultrasmall Au clusters. It is suggested that diphosphines provide a set of flexible ligands to allow size-controlled synthesis of Au nanoparticles.     

Optical properties of systems containing Au55-clusters

Gold cluster compounds were investigated which contain clusters of 55 gold atoms in each unit. The ligands stabilize these clusters and, hence, many-cluster systems can be prepared which mainly show the properties of the single dressed cluster. Experimental results of optical and electron-microscopical investigations are presented and shortly discussed in view of the question whether the clusters are molecular or solid-state like.     

Reaction of Au(55)(PPh(3))(12)Cl(6) with thiols yields thiolate monolayer protected Au(75) clusters

This paper describes the reaction of the phosphine-protected Au nanoparticle Au(55)(PPh(3))(12)Cl(6) (1, "Au55") with hexanethiol (2) and other thiols. The voltammetry of the reaction product 2 displays a well-defined pattern of peaks qualitatively reminiscent of Au(38) nanoparticles, but with quite different spacing (0.74 +/- 0.01 V) between the potentials of initial oxidation and reduction steps (electrochemical gap). Correction of this "molecule-like" gap for charging energy indicates a HOMO-LUMO gap energy of about 0.47 V. Voltammetry of the products (3 and 4) of reaction of 1 with C(3)H(7)SH and PhC(2)H(4)SH, respectively, is similar. Laser desorption/ionization mass spectrometry (LDI-MS) shows that 2 contains a high proportion of a core mass in the 14-15 kDa range, which is proposed to be Au(75). UV-vis spectra of 2-4 are relatively featureless, similar to previous reports of thiolate-protected Au(75) nanoparticles. HPLC analysis of 2 shows a Au(75) content of ca. 73%; the electrochemical purity estimate is also high, about 55%. Combining the mass spectrometric result with thermogravimetric analysis of 2 leads to a preliminary formulation Au(75)(SC(6)H(13))(40). This Au(75) synthesis complements a previous Brust-type synthesis and is unusual in the apparent provocation in the reaction of an increase in core size.     

Model catalysts of supported Au nanoparticles and mass-selected clusters

In surface science, much effort has gone into obtaining a deeper understanding of the size-selectivity of nanocatalysts. In this article, electronic and chemical properties of various model catalysts consisting of Au are reported. Au supported by oxide surfaces becomes inert towards chemisorption and oxidation as the particle size became smaller than a critical size (2-3 nm). The inertness of these small Au nanoparticles is due to the electron-deficient nature of smaller Au nanoparticles, which is a result of metal-substrate charge transfer. Properties of Au clusters smaller than ～20 atoms were shown to be non-scalable, i.e., every atom can drastically change the chemical properties of the clusters. Moreover, clusters with the same size can show dissimilar properties on various substrates. These recent endeavours show that the activity of a catalyst can be tuned by varying the substrate or by varying the cluster size on an atom-by-atom basis.