Symmetry and Electronic Structure of Noble-Metal Nanoparticles and the Role of Relativity

Häkkinen, Hannu; Moseler, Michael; Kostko, Oleg; Morgner, Nina; Hoffmann, M.; Issendorff, Bernd von

doi:10.1103/physrevlett.93.093401

Cited by 250 publications

(242 citation statements)

References 33 publications

(50 reference statements)

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“…This structural assignment method has been widely used on cluster study. 4,31,39,[41][42][43][44][45][46] EA is calculated as the difference between the total energies of the neutral and anion at their respective optimized structures. The theoretical DOS spectra are shifted by setting the HOMO level of the spectra to give the negative of VDE value for the complex.…”

Section: Assignments Of the Complex Structuresmentioning

confidence: 99%

Phenyl-Coinage Metal (Ag, Au) Complexes: an Anion Photoelectron Spectroscopy and Density Functional Study

et al. 2005

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The important intermediate phenyl-coinage metal complexes (Ag m C 6 H 5 -, Au m C 6 H 5 -), which are produced from the reactions between coinage metal clusters formed by laser ablation and the benzene molecules seeded in argon carrier gas, are studied by PES (photoelectron spectroscopy) and DFT (density functional theory). The EAs (adiabatic electron affinities) of these complexes are obtained from PES at both 308 and 193 nm photon energies and show odd-even alternation. Calculations with DFT are carried out on the structural and electronic properties of Ag m C 6 H 5 -and Au m C 6 H 5 -; the adiabatic detachment energy and the calculated DOS (density of states) for the ground state of a given anion are in good agreement with the experimental PES results. The observed spectra are also compared with those of the pure coinage metal clusters, which reveal that there are some similarities between them and the phenyl acts like an additional metal atom in the clusters. Furthermore, the bonding between phenyl and metal is analyzed, suggesting that phenyl group binds perpendicularly on metal clusters through C-M σ bond.

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Section: Assignments Of the Complex Structuresmentioning

confidence: 99%

Phenyl-Coinage Metal (Ag, Au) Complexes: an Anion Photoelectron Spectroscopy and Density Functional Study

et al. 2005

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“…In addition to these structures, structures expected to exist from the experimental photoelectron spectra 29,30,31,32,33 and those expected to exist in the neighborhood of the local minimum points on the potential energy surface from our experience of the optimization procedures for these systems 18 were selected. The optimized structures of Na N and Cu N obtained in this study were employed as the initial structures of Ag N in the geometry optimization procedure, and the interatomic distances satisfying the nearest neighbor atomic distance ratio between the Na, Cu, and Ag bulk crystals were scaled.…”

Section: Methodsmentioning

confidence: 99%

Comprehensive study of sodium, copper, and silver clusters over a wide range of sizes 2≤N≤75

Itoh

Kumar

Adschiri³

et al. 2009

The Journal of Chemical Physics

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The geometric and electronic structures of NaN , CuN , and AgN metal clusters are systematically studied based on the density functional theory over a wide range of cluster sizes 2 ≤ N ≤ 75. A remarkable similarity is observed between the optimized geometric structures of alkali and noble metal clusters over all of the calculated cluster sizes N . The most stable structures are the same for the three different metal clusters for approximately half the cluster sizes N considered in this study. Even if the most stable structures are different, the same types of structures are obtained when the meta-stable structures are also considered. For all of the three different metal clusters, the cluster shapes change in the order of linear, planar, opened, and closed structures with increasing N . This structural type transition leads to a deviation from the monotonic increase in the volume with N . A remarkable similarity is also observed for the N dependence of the cluster energy E(N ) for the most stable geometric structures. The amplitude of this energy difference is larger in the two noble metal clusters than in the alkali metal cluster. This is attributed to the contribution of d electrons to the bonds. The magic number is defined in the framework of total energy calculations for the first time. In the case of NaN , a semi-quantitative comparison between the experimental abundance spectra (Knight et al., Phys. Rev. Lett. 52, 2141Lett. 52, (1984) and the total energy calculations is carried out. The changing aspect of the Kohn-Sham eigenvalues from N = 2 to N = 75 is presented for the three different metal clusters. The feature of the bulk density of states already appears at N = 75 for all of three clusters. With increasing N , the HOMO-LUMO gap clearly exhibits an odd-even alternation and converges to 0. Although there is a similarity in the N dependence of the HOMO-LUMO gap between the three metal clusters, it is much stronger between the two noble metal clusters. The growth aspect of the d band below the Fermi level of the noble metal clusters with increasing N is presented. A good correspondence is observed in the d characteristic of the electronic states between the cluster composed of 75 atoms and the bulk metal. The similarities observed in the N dependence of the geometric structures and E(N )s originate from the similarity in that of the electronic structures.

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“…We discuss the relevance of our findings with respect to identification of the precise compositions of other known allthiolate-protected gold clusters, as well as the importance of the atomic structure of the interface of the gold core and the goldthiolate shell in compounds 1 and 2 regarding the structure of the interface of the bulk Au(111) and the self-assembled monolayer (SAM). The theoretical concepts laid out here provide a solid background for further understanding of the distinct electrical, optical, and chemical properties of the stable monolayer-protected Au nanoclusters (MPCs) (18)(19)(20)(21)(22)(23)(24)(25)(26)(27)(28)(29)(30), which eventually can parallel the wealth of information gained from investigations of nanosized gold clusters in the gas phase (10,11,(31)(32)(33)(34)(35) and should facilitate engineering of nano-applications, made out of MPC building blocks, for catalysis, sensing, photonics, biolabeling, and molecular electronics.…”

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confidence: 99%

A unified view of ligand-protected gold clusters as superatom complexes

Walter¹,

Akola

Lopez-Acevedo³

et al. 2008

Proc. Natl. Acad. Sci. U.S.A.

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1,545

2,167

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Synthesis, characterization, and functionalization of self-assembled, ligand-stabilized gold nanoparticles are long-standing issues in the chemistry of nanomaterials. Factors driving the thermodynamic stability of well documented discrete sizes are largely unknown. Herein, we provide a unified view of principles that underlie the stability of particles protected by thiolate (SR) or phosphine and halide (PR 3, X) ligands. The picture has emerged from analysis of large-scale density functional theory calculations of structurally characterized compounds, namely Au 102(SR)44, Au39(PR3)14X6 ؊ , Au 11(PR3)7X3, and Au13(PR3)10X2 3؉ , where X is either a halogen or a thiolate. Attributable to a compact, symmetric core and complete steric protection, each compound has a filled spherical electronic shell and a major energy gap to unoccupied states. Consequently, the exceptional stability is best described by a ''noble-gas superatom'' analogy. The explanatory power of this concept is shown by its application to many monomeric and oligomeric compounds of precisely known composition and structure, and its predictive power is indicated through suggestions offered for a series of anomalously stable cluster compositions which are still awaiting a precise structure determination.density functional theory ͉ monolayer-protected cluster

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Symmetry and Electronic Structure of Noble-Metal Nanoparticles and the Role of Relativity

Cited by 250 publications

References 33 publications

Phenyl-Coinage Metal (Ag, Au) Complexes: an Anion Photoelectron Spectroscopy and Density Functional Study

Phenyl-Coinage Metal (Ag, Au) Complexes: an Anion Photoelectron Spectroscopy and Density Functional Study

Comprehensive study of sodium, copper, and silver clusters over a wide range of sizes 2≤N≤75

A unified view of ligand-protected gold clusters as superatom complexes

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