Gold Sulfide Nanoclusters: A Unique Core‐In‐Cage Structure

Jiang, De‐en; Walter, Michael; Dai, Sheng

doi:10.1002/chem.201000327

Cited by 35 publications

(47 citation statements)

References 62 publications

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“…In addition, several heteroatomic clusters have been studied using BH-DFT. Generally, FP-BH studies have been used to investigate the influence of a single main-group element, [176] transition metal, [177,208]22 or a few sulfur [175] atoms on the geometric and electronic structure of Au clusters. A little different and, from a chemical point of view, more instructive, is the case study by Gao et al [174] moiety.…”

Section: Basin Hoppingmentioning

confidence: 99%

Global optimization of clusters using electronic structure methods

Heiles

Johnston

2013

Int J of Quantum Chemistry

198

191

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Over the past decade, there has been a significant growth in the development and application of methods for performing global optimization (GO) of cluster and nanoparticle structures using first-principles electronic structure methods coupled to sophisticated search algorithms. This has in part been driven by the desire to avoid the use of empirical potentials (EPs), especially in cases where no reliable potentials exist to guide the search toward reasonable regions of configuration space. This has been facilitated by improvements in the reliability of the search algorithms, increased efficiency of the electronic structure methods, and the development of faster, multiprocessor high-performance computing architectures. In this review, we give a brief overview of GO algorithms, though concentrating mainly on genetic algorithm and basin hopping techniques, first in combination with EPs. The major part of the review then deals with details of the implementation and application of these search methods to allow exploration for global minimum cluster structures directly using electronic structure methods and, in particular, density functional theory. Example applications are presented, ranging from isolated monometallic and bimetallic clusters to molecular clusters and ligated and surface supported metal clusters. Finally, some possible future developments are highlighted.

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Section: Basin Hoppingmentioning

confidence: 99%

Global optimization of clusters using electronic structure methods

Heiles

Johnston

2013

Int J of Quantum Chemistry

198

191

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“…19 The choice of the PBE functional is justified since it has been shown that other meta-GGA functionals, such as the nonempirical Tao-Perdew-Staroverov-Scuseria (TPSS) and the M06L one, provide similar trends in the relative energies of gold sulfide nanoclusters. 20 Structural optimizations were performed without symmetry restrictions, using a force tolerance criterion of 0.01 eV Å…”

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confidence: 99%

On the structure of the Au18(SR)14 cluster

Tlahuice

Garzón

2012

Phys. Chem. Chem. Phys.

104

158

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First principles calculations are used for a systematic search of the lowest-energy (most-stable) structure of the recently synthesized Au 18 (SR) 14 cluster. A comparison of the calculated optical absorption and electronic circular dichroism spectra, which are highly sensitive to the cluster structure and chirality, with the experimental spectra of the glutathione-protected gold cluster, Au 18 (SG) 14 , is used to discriminate between low-energy isomers of the Au 18 (SR) 14 (R = CH 3 ) cluster. From the good agreement between calculated and measured spectra, it is predicted that the structure of the Au 18 (SR) 14 cluster consists of a prolate Au 8 core covered with two dimer (SR-Au-SR-Au-SR) and two trimer (SR-Au-SR-Au-SR-Au-SR) motifs. These results provide additional evidence on the existence of longer trimer motifs as protecting units of small thiolated gold clusters.Studies on ligand-protected metal clusters became an important field of research due to their interesting properties and promising applications in nanotechnology. 1 Despite the tremendous progress achieved during the past fifteen years on the synthesis and physicochemical characterization of small (o2 nm) thiolateprotected gold clusters, several issues of scientific and technological interest still remain unknown. 1 One of the challenges is to develop and improve the synthetic chemistry for synthesizing a series of size-discrete Au n (SR) m clusters with high purity and high yield, followed by their crystallization and X-ray total structure determination, 1 as was the case for (n,m) = (25,18), (38,24), and (102,44). 2-4 A precise knowledge of the cluster atomic structure is a fundamental step toward a full understanding of other physicochemical properties of thiolated gold clusters. [1][2][3][4] Gold clusters covered by glutathione, Au n (SG) m , and other related ligands had been synthesized and size-separated by Tsukuda's group. 5,6 High mass resolution and accurate mass calibration in their electrospray ion mass spectrometry (ESI-MS) data allowed the exact determination of the cluster chemical composition. 5,6 The nine smallest compounds were assigned to cluster sizes with n : m ratio: 10 : 10, 15 : 13, 18 : 14, 22 : 16, 22 : 17, 25 : 18, 29 : 20, 33 : 22, and 39 : 24, respectively. 5,6 Interestingly, the most abundant compound with enhanced stability against unimolecular decomposition was found to be the Au 18 (SG) 14 cluster, 5 although it also had been shown that the 25 : 18 clusters exhibit the highest stability against core etching. 7More recently, Dass' group has synthesized a mixture of thiolated gold clusters, Au n (RS) m (R = CH 2 CH 2 Ph), in the Au 16 -Au 31 size range using a surfactant-free synthesis method. 8 Again, the most abundant cluster size in the mixture, detected by matrix-assisted laser desorption time of flight mass spectrometry (MALDI-TOF-MS), corresponded to the Au 18 (SR) 14 cluster. 8 It is expected that the peculiar stability and higher relative abundance of the 18 : 14 cluster should motivate its crystallizat...

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“…The spectra at Au L 3 -edge were obtained at five different zones probed by an X-ray beam size of 0.05 mm x 0.05 mm, while flowing the precursor solutions into the channels. Based on these spectra analysis, the first changes in the precursor solution was found to take place around the zone 5 with the formation of Au x S y -nanoclusters 21 having an Au/S ratio close to 2 with Au(I) oxidation state. Fig.…”

Section: Representative Resultsmentioning

confidence: 98%

Millifluidics for Chemical Synthesis and Time-resolved Mechanistic Studies

Krishna

Biswas

Navin

et al. 2013

JoVE

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Procedures utilizing millifluidic devices for chemical synthesis and time-resolved mechanistic studies are described by taking three examples. In the first, synthesis of ultra-small copper nanoclusters is described. The second example provides their utility for investigating time resolved kinetics of chemical reactions by analyzing gold nanoparticle formation using in situ X-ray absorption spectroscopy. The final example demonstrates continuous flow catalysis of reactions inside millifluidic channel coated with nanostructured catalyst. Video LinkThe video component of this article can be found at

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Gold Sulfide Nanoclusters: A Unique Core‐In‐Cage Structure

Cited by 35 publications

References 62 publications

Global optimization of clusters using electronic structure methods

Global optimization of clusters using electronic structure methods

On the structure of the Au18(SR)14 cluster

Millifluidics for Chemical Synthesis and Time-resolved Mechanistic Studies

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