Search results for "Clusters"
showing 10 items of 1274 documents
Electronic and vibrational spectroscopic studies of gold-nanoclusters
2016
Gold nanoclusters are a peculiar new material with properties between that of bulk metal and single atoms. They show size-dependent evolution of optical and electronic properties sensitive to the change of single atom or single electron in the system. Understanding the relationship between structure and properties is important to both fundamental scientific question of the role of the quantum size effects in small metal-clusters, and to application of nanoclusters in e.g. photonics, nanoelectronics, and heterogeneous catalysis. In this thesis four spectroscopic studies of monolayer-protected gold-nanoclusters are presented. The optical gap of the Au144(PET)60 and (Au/Ag)144(PET)60 (PET: pheny…
Copper-hydride nanoclusters with enhanced stability by N-heterocyclic carbenes
2021
AbstractCopper-hydrides have been intensively studied for a long time due to their utilization in a variety of technologically important chemical transformations. Nevertheless, poor stability of the species severely hinders its isolation, storage and operation, which is worse for nano-sized ones. We report here an unprecedented strategy to access to ultrastable copper-hydride nanoclusters (NCs), namely, using bidentate N-heterocyclic carbenes as stabilizing ligands in addition to thiolates. In this work, a simple synthetic protocol was developed to synthesize the first large copper-hydride nanoclusters (NCs) stabilized by N-heterocyclic carbenes (NHCs). The NC, with the formula of Cu31(RS)2…
Thiol-Stabilized Atomically Precise, Superatomic Silver Nanoparticles for Catalyzing Cycloisomerization of Alkynyl Amines
2018
Abstract Both the electronic and surface structures of metal nanomaterials play critical roles in determining their chemical properties. However, the non-molecular nature of conventional nanoparticles makes it extremely challenging to understand the molecular mechanism behind many of their unique electronic and surface properties. In this work, we report the synthesis, molecular and electronic structures of an atomically precise nanoparticle, [Ag206L72]q (L = thiolate, halide; q = charge). With a four-shell Ag7@Ag32@Ag77@Ag90 Ino-decahedral structure having a nearly perfect D5h symmetry, the metal core of the nanoparticle is co-stabilized by 68 thiolate and 4 halide ligands. Both electroche…
Ag44(EBT)26(TPP)4 Nanoclusters with Tailored Molecular and Electronic Structure
2021
Although atomically precise metalloid nanoclusters (NCs) of identical size with distinctly different molecular structures are highly desirable to understand the structural effects on the intriguing optical and photophysical properties, their synthesis remains highly challenging. Herein, we employed phosphine and thiol capping ligands featuring appropriate steric effects and synthesized a charge‐neutral Ag NC with the formula, Ag 44 (EBT) 26 (TPP) 4 (EBT: 2‐ethylbenzenethiolate; TPP: triphenylphosphine). The single‐crystal X‐ray structure reveals that this NC has a hollow metal core of Ag 12 @Ag 20 and a metal‐ligand shell of Ag 12 (EBT) 26 (TPP) 4 . The presence of mixed ligands and long V‐…
Electronic shell structures in bare and protected metal nanoclusters
2016
This short review discusses the concept of the electronic shell structure in the context of metal nanoclusters. Electronic shell structure is a natural consequence of quantization of fermionic states in a quantum confinement, where the symmetry of the confining potential creates energetically close-lying sets of states that reflect the symmetry of the potential. It was introduced in cluster physics in early 1980s and initially influenced greatly by the related model of nuclear shell structure from 1950’s. Three application areas are discussed consisting of free gas phase clusters, clusters supported by insulating oxides or oxide thin films, and clusters that are synthesized by wet chemistry…
[Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster
2016
Engineering the surface ligands of metal nanoparticles is critical in designing unique arrangements of metal atoms. Here, we report the synthesis and total structure determination of a large box-shaped Ag67 nanocluster (NC) protected by a mixed shell of thiolate (2,4-dimethylbenzenethiolate, SPhMe2) and phosphine (triphenylphosphine, PPh3) ligands. Single crystal X-ray diffraction (SCXRD) and electrospray ionization mass spectrometry (ESI-MS) revealed the cluster formula to be [Ag67(SPhMe2)32(PPh3)8]3+. The crystal structure shows an Ag23 metal core covered by a layer of Ag44S32P8 arranged in the shape of a box. The Ag23 core was formed through an unprecedented centered cuboctahedron, i.e.,…
Bulky Surface Ligands Promote Surface Reactivities of [Ag141X12(S-Adm)40]3+ (X=Cl, Br, I) Nanoclusters: Models for Multiple-Twinned Nanoparticles
2017
Surface ligands play important roles in controlling the size and shape of metal nanoparticles and their surface properties. In this work, we demonstrate that the use of bulky thiolate ligands, along with halides, as the surface capping agent promotes the formation of plasmonic multiple-twinned Ag nanoparticles with high surface reactivities. The title nanocluster [Ag141X12(S-Adm)40]3+ (where X = Cl, Br, I; S-Adm = 1-adamantanethiolate) has a multiple-shell structure with an Ag71 core protected by a shell of Ag70X12(S-Adm)40. The Ag71 core can be considered as 20 frequency-two Ag10 tetrahedra fused together with a dislocation that resembles multiple-twinning in nanoparticles. The nanocluster…
Theoretical investigation of the electronic structure of fullerenes
1994
Summary form only given. Research in the growing family of fullerene compounds are in continuous expansion. Much theoretical and experimental effort has been devoted to the study of the electronic properties these carbon cages present. However, although significant work has been done, the purpose of this paper is to provide a detailed theoretical analysis of the electronic properties of several fullerenes. We have calculated the electronic structure of these carbon cages within the valence effective Hamiltonian (VEH) approach. The calculated one-electron energy levels are correlated with experimental UPS spectra. The good correlation between calculated and experimental values shows VEH appr…
Towards Controlled Synthesis of Water-Soluble Gold Nanoclusters : Synthesis and Analysis
2019
Water-soluble gold nanoclusters with well-defined molecular structures and stability possess particular biophysical properties making them excellent candidates for biological applications as well as for fundamental spectroscopic studies. The currently existing synthetic protocols for atomically monodisperse thiolate-protected gold nanoclusters (AuMPCs) have been widely expanded with organothiolates, yet the direct synthesis reports for water-soluble AuMPCs are still deficient. Here, we demonstrate a wet-chemistry pH-controlled synthesis of two large water-soluble nanoclusters utilizing p-mercaptobenzoic acid (pMBA), affording different sizes of plasmonic AuMPCs on the preparative scale (∼7 …
A novel heuristic memetic clustering algorithm
2013
In this paper we introduce a novel clustering algorithm based on the Memetic Algorithm meta-heuristic wherein clusters are iteratively evolved using a novel single operator employing a combination of heuristics. Several heuristics are described and employed for the three types of selections used in the operator. The algorithm was exhaustively tested on three benchmark problems and compared to a classical clustering algorithm (k-Medoids) using the same performance metrics. The results show that our clustering algorithm consistently provides better clustering solutions with less computational effort.