Search results for "Nanoclusters"
showing 10 items of 164 documents
Solvent-mediated assembly of atom-precise gold–silver nanoclusters to semiconducting one-dimensional materials
2020
Bottom-up design of functional device components based on nanometer-sized building blocks relies on accurate control of their self-assembly behavior. Atom-precise metal nanoclusters are well-characterizable building blocks for designing tunable nanomaterials, but it has been challenging to achieve directed assembly to macroscopic functional cluster-based materials with highly anisotropic properties. Here, we discover a solvent-mediated assembly of 34-atom intermetallic gold–silver clusters protected by 20 1-ethynyladamantanes into 1D polymers with Ag–Au–Ag bonds between neighboring clusters as shown directly by the atomic structure from single-crystal X-ray diffraction analysis. Density fun…
Au25(SEt)18 a nearly naked thiolate-protected Au25 cluster Struct. analysis by single crystal X-ray crystallograp. and electron nuclear double res
2014
X-ray crystallography has been fundamental in discovering fine structural features of ultrasmall gold clusters capped by thiolated ligands. For still unknown structures, however, new tools capable of providing relevant structural information are sought. We prepared a 25-gold atom nanocluster protected by the smallest ligand ever used, ethanethiol. This cluster displays the electrochemistry, mass spectrometry, and UV-vis absorption spectroscopy features of similar Au25 clusters protected by 18 thiolated ligands. The anionic and the neutral form of Au25(SEt)18 were fully characterized by (1)H and (13)C NMR spectroscopy, which confirmed the monolayer's properties and the paramagnetism of neutr…
Point Group Symmetry Analysis of the Electronic Structure of Bare and Protected Metal Nanocrystals
2018
The electronic structures of a variety of experimentally identified gold and silver nanoclusters from 20 to 246 atoms, either unprotected or protected by several types of ligands, are characterized by using point group specific symmetry analysis. The delocalized electron states around the HOMO-LUMO energy gap, originating from the metal s-electrons in the cluster core, show symmetry characteristics according to the point group that describes best the atomic arrangement of the core. This indicates strong effects of the lattice structure and overall shape of the metal core to the electronic structure, which cannot be captured by the conventional analysis based on identification of spherical a…
Gold nanoclusters for ratiometric sensing of pH in extremely acidic media.
2019
AuNCs capped with β-nicotinamide adenine dinucleotide phosphate exhibit an outstanding performance as fluorescent pH sensors; specifically they exhibit a high emission in strongly acidic media and linear dependence on pH in extremely acidic media (0.6–2.7) as well as in the 7.0–9.2 pH range, while they are unresponsive at intermediate pH values. Remarkably, these AuNCs make ratiometric sensing possible in extremely acidic media with a single fluorophore, specifically the nanocluster itself.
Analysis of the Electronic Structure of Non-Spherical Ligand-Protected Metal Nanoclusters: The Case of a Box-Like Ag67
2016
In this work we introduce a new strategy to investigate the electronic shell structure of ligand-protected metal nanoclusters of polyhedral core shape. The central idea is to identify the symmetry of the Kohn–Sham molecular orbitals of an atomistic structure based on their projection onto the electronic states of a jellium system with a similar shape of the background charge density. Herein, we study the connection between a reduced atomistic model of the recently reported box-like [Ag67(SR)32(PR3)8]3+ nanocluster and a jellium box consisting of 32 free electrons. With this approach, we determine the symmetry of electronic states of the metal core and identify those that are involved in the…
Influence of metal–support interaction on the surface structure of gold nanoclusters deposited on native SiOx/Si substrates
2014
The structure of small gold nanoclusters (R ~ 2.5 nm) deposited on different silica on silicon substrates is investigated using several characterization techniques (AFM, XRD, EXAFS and GISAXS). The grain morphology and the surface roughness of the deposited gold clusters are determined by AFM. The in-plane GISAXS intensity is modelled in order to obtain information about the cluster size and the characteristic length scale of the surface roughness. AFM and GISAXS results are in excellent agreement and show that the surface morphology of the deposited clusters depends on whether defect-rich (native) or defect-free (thermal) silica is used as a substrate. Gold clusters show a strong tendency …
Ab Initio Simulation of Clusters: Relativistic Effects in Structure and Bonding of Noble Metal Nanoparticles
2005
Resolving the atomic and electronic structures of nanoclusters represents an important preliminary for their controlled use in future nanotechnologies. Here we show through the comparison of density-functional calculations with high-resolution photoelectron spectroscopy that 1.4 nm nanoparticles of silver (negatively charged clusters of 53 to 58 atoms) are icosahedral-based structures displaying a perfect icosahedral-induced electronic shell structure for Ag 55 − and slightly perturbed shell structures for the neighboring cluster sizes. At variance, 55-atom gold clusters exhibit several isomeric structures of low symmetry, with a largely diminished electronic shell structure. This surprisin…
Magnetic properties of colloidal cobalt nanoclusters
2010
Abstract. Co nanoclusters were synthesized by an inverse-micelle chemical route. The magnetic and microstructural properties of the nanoparticles have been analyzed as a function of the surfactant (AOT and DEHP) and the drying method. Microstructural analysis has been performed by TEM and XANES; magnetic properties have been studied by hysteresis loops and zero-field cooling - field cooling (ZFC-FC) curves. TEM images show 2 to 4 nm sized particles spherical in shape. XANES measurements point out a significant presence of Co3O4 with metallic Co and some Co2+ bound to the surfactant. The presence of antiferromagnetic Co3O4 explains the magnetic transition observed at low T in both ZFC-FC mea…
Combinatorial Identification of Hydrides in a Ligated Ag40 Nanocluster with Noncompact Metal Core
2019
No formation of bulk silver hydride has been reported. Until very recently, only a few silver nanoclusters containing hydrides have been successfully prepared. However, due to the lack of effective techniques and also poor stability of hydride-containing Ag nanoclusters, the identification of hydrides' location within Ag nanoclusters is challenging and not yet achieved, although some successes have been reported on clusters of several Ag atoms. In this work, we report a detailed structural and spectroscopic characterization of the [Ag40(DMBT)24(PPh3)8H12]2+ (Ag40H12) cluster (DMBT = 2,4-dimethylbenzenethiol). The metal framework consists of three concentric shells of Ag8@Ag24@Ag8, which can…
Optical active centres in ZnO samples
2006
Abstract In recent years, there has been a resurgence in the interest in the use of ZnO (Eg ∼ 3.37 eV) as a material for a wide range of opto-emitter applications spanning visible and short wavelengths. Bulk, thin films and nanomaterials obtained using different synthesis methods have been investigated for optoelectronic and biotechnological device applications. Nominally undoped bulk samples typically present a myriad-structured near-band-edge recombination, mainly due to free/bound excitons and donor–acceptor pair transitions. Furthermore, deep level emission due to intrinsic defects and extrinsic impurities, such as transition metal ions, are commonly observed in different grades of bulk…