Search results for "METAL CLUSTERS"
showing 10 items of 32 documents
Prospects and challenges for computer simulations of monolayer-protected metal clusters
2021
Precise knowledge of chemical composition and atomic structure of functional nanosized systems, such as metal clusters stabilized by an organic molecular layer, allows for detailed computational work to investigate structure-property relations. Here, we discuss selected recent examples of computational work that has advanced understanding of how these clusters work in catalysis, how they interact with biological systems, and how they can make self-assembled, macroscopic materials. A growing challenge is to develop effective new simulation methods that take into account the cluster-environment interactions. These new hybrid methods are likely to contain components from electronic structure t…
Semiclassical Methods for the Description of Large Metal Clusters
1996
One of the most fascinating aspects of clusters is that they can be made arbitrarily large and therefore provide links between the microscopic and the macroscopic world. It is challenging to study how their physical properties change when going from atoms and small molecules to the bulk limit of condensed matter. But also the models and mathematical tools themselves, which are used in order to tackle the many-body problem, are an object of study for the theoretician. In particular, the question of how far quantum-mechanics must be carried with increasing size and where classical pictures become appropriate is of great interest. In this spirit, we discuss here some semiclassical methods for …
The MOF-driven synthesis of supported palladium clusters with catalytic activity for carbene-mediated chemistry
2016
The development of catalysts able to assist industrially important chemical processes is a topic of high importance. In view of the catalytic capabilities of small metal clusters, research efforts are being focused on the synthesis of novel catalysts bearing such active sites. Here we report a heterogeneous catalyst consisting of Pd4 clusters with mixed-valence 0/+1 oxidation states, stabilized and homogeneously organized within the walls of a metal-organic framework (MOF). The resulting solid catalyst outperforms state-of-the-art metal catalysts in carbene-mediated reactions of diazoacetates, with high yields (>90%) and turnover numbers (up to 100,000). In addition, the MOF-supported Pd4 c…
Electrocrystallization of Monolayer-Protected Gold Clusters : Opening the Door to Quality, Quantity, and New Structures
2017
Thiolate-protected metal clusters are materials of ever-growing importance in fundamental and applied research. Knowledge of their single-crystal X-ray structures has been instrumental to enable advanced molecular understanding of their intriguing properties. So far, however, a general, reliable, chemically clean approach to prepare single crystals suitable for accurate crystallographic analysis was missing. Here we show that single crystals of thiolate-protected clusters can be grown in large quantity and very high quality by electrocrystallization. This method relies on the fact that charged clusters display a higher solubility in polar solvents than their neutral counterparts. Nucleation…
Pulsed photodissociation in an ion cyclotron resonance trap: extending the time range for unimolecular dissociation studies of metal clusters
1997
Real-Time Observation of “Soft” Magic-Size Clusters during Hydrolysis of the Model Metallodrug Bismuth Disalicylate
2021
International audience; Colloidal bismuth therapeutics have been used for hundreds of years, yet remain mysterious. Here we report an X-ray pair distribution function (PDF) study of the solvolysis of bismuth disalicylate, a model for the metallodrug bismuth subsalicylate (Pepto-Bismol). This reveals catalysis by traces of water, followed by multistep cluster growth. The ratio of the two major species, {Bi9O7} and {Bi38O44}, depends on exposure to air, time, and the solvent. The solution-phase cluster structures are of significantly higher symmetry in comparison to solid-state analogues, with reduced off-center Bi3+ displacements. This explains why such “magic-size” clusters can be both stab…
High-spin states in tetrahedral X4 clusters (X = H, Li, Na, K)
2010
The high-spin electronic states for lithium, sodium, and potassium four-atom clusters were studied. In particular, we performed coupled cluster geometry optimization of the quintet state in tetrahedral geometry. The quintet state of these systems is characterized by having all the valence electron Unpaired, giving rise to the so-called no-pair bonding. Single-point full configuration interaction computations on the equilibrium geometries for the various Clusters are also presented. The analysis of the valence orbitals in a localized representation confirms the importance of the p atomic orbitals to explain this unusual type of bond. (C) 2009 Wiley Periodicals, Inc. Int J Quantum Chem 110: 8…
Enhanced Surface Ligands Reactivity of Metal Clusters by Bulky Ligands for Controlling Optical and Chiral Properties.
2021
Surface ligands play critical roles in determining the surface properties of metal clusters. However, modulating the properties and controlling the surface structure of clusters through surface‐capping agent displacement remain a challenge. In this work, a silver cluster, [Ag 14 (SPh(CF 3 ) 2 ) 12 (PPh 3 ) 4 (DMF) 4 ] ( Ag 14 ‐DMF , where HSPh(CF 3 ) 2 is 3,5‐bis(trifluoromethyl)benzenethiol, PPh 3 is triphenylphosphine and DMF is N,N‐Dimethylformamide), with weakly coordinated DMF ligands on the surface silver sites, was synthesized by using a mixed ligands strategy (bulky thiolates, phosphines and small solvents). The as‐prepared Ag 14 ‐DMF is a racemic mixture of chiral molecules. Owing …
Electronic Shell Structure in Icosahedral Metal Clusters
1992
The shell structure of valence electrons in icosahedral and cuboctahedral simple metal clusters is studied using the free electron model and the Huckel model. The shell structure in a 1415 atom icosahedral cluster has still similarities with that of a spherical cluster. The effect of the finite temperature on the shell structure in liquid clusters is discussed.