Search results for "Clusters"
showing 10 items of 1274 documents
Gold assisted oxygen dissociation on a molybdenum-doped CaO(001) surface
2016
Using density functional theory (DFT) calculations, we address the adsorption of O2 and the coadsorption of gold species and oxygen molecules on a Mo-doped CaO(001) surface with 1.25% impurity concentration. With the help of the Born–Haber thermodynamic cycle, the enhanced binding of an oxygen molecule on Ca(Mo)O is attributed to energy gain owing to simultaneous electron transfer from the dopant to the molecule and lattice relaxations. We consider three coadsorption structures for an Au atom and O2 molecule with different Au–O2 distances. The calculations demonstrate that the coadsorption structures take one electron from the dopant and the O–Au–O chain structure is thermodynamically more …
Magneto-structural correlations and DFT calculations in two rare tetranuclear copper(II)-clusters with doubly phenoxo and end-on azido bridges: Synth…
2010
International audience; By slightly changing the synthetic conditions, we have prepared two closely related linear tetranuclear CuII complexes with the symmetrical ONNO donor tetradentate Schiff-base ligand [H2L = (OH)C6H4(CH3)Cdouble bond; length as m-dashN(CH2)3Ndouble bond; length as m-dashC(CH3)C6H4(OH)] and with azide ions. These two distinctly coloured crystalline products were characterized by elemental analysis, IR and UV–Vis spectroscopy, CV, EPR spectra and variable temperature magnetic measurements. Single crystal X-ray diffraction studies of the green [Cu4(μ-L)2(μ1,1-N3)2(N3)2] (1) and the red [Cu4(μ-L)2(μ1,1-N3)2(N3)2(H2O)2] (2) crystals show that the coordination environment o…
Chiral Inversion of Thiolate-Protected Gold Nanoclusters via Core Reconstruction without Breaking an Au-S Bond
2019
Based on density functional theory computations of the well-known chiral Au38(SR)24 nanocluster and its Pd- and Ag-doped derivatives, we propose here a mechanism for chiral inversion that does not require breaking of a metal-sulfur bond at the metal-ligand interface, but features a collective rotation of the gold core. The calculated energy barriers for this mechanism for Au38 and Pddoped Au38 are in the range of 1 – 1.5 eV, significantly lower than barriers involving breakage of Au-S bonds (2.5 eV). For Ag-doped Au38, barriers for both mechanisms are similar (1.3 – 1.5 eV). Inversion barriers for a larger chiral Au144(SR)60 are much higher (2.8 eV). Our computed barriers are in a good agre…
Solubility-Driven Isolation of a Metastable Nonagold Cluster with Body-Centered Cubic Structure.
2020
The conventional synthetic methodology of atomically precise gold nanoclusters using reduction in solutions offers only thermodynamically most stable nanoclusters. We report herein a solubility‐driven isolation strategy to access the synthesis of a metastable gold cluster. The cluster, with the composition of [Au 9 (PPh 3 ) 8 ] + ( 1 ), displays an unusual, nearly perfect body‐centered‐cubic (bcc) structure. As revealed by ESI‐MS and UV/Vis measurement, the cluster is metastable in solution and converts to the well‐known [Au 11 (PPh 3 ) 8 Cl 2 ] + ( 2 ) within just 90 min. DFT calculations revealed that while both 1 and 2 are eight‐electron superatoms, there is a driving force to convert 1 …
Multivariate statistical analysis of heavy metals and physico-chemical parameters in the groundwater of Karak District, Khyber Pakhtunkhwa, Pakistan
2021
Groundwater heavy metal pollution is a major concern all around the world. For the assessment of heavy metals and physico-chemical characteristics. groundwater samples were collected from different locations of the Karak District, Pakistan. With the help of the global information system device (GIS), groundwater samples were collected and studied from 47 locations. The present study focused on the water table (WT), water source depth (WSD), pH, electrical conductivity (EC), dissolved oxygen (DO), total dissolved solids (TDS), lead (Pb(II)), silver (Ag(I)), iron (Fe(II)) and chromium (Cr(VI)) parameters. Heavy metals were analyzed by the Atomic Absorption Spectrophotometer (AAS). The Pearson…
Chloride ligands on DNA-stabilized silver nanoclusters
2023
DNA-stabilized silver nanoclusters (AgN-DNAs) are known to have one or two DNA oligomer ligands per nanocluster. Here, we present the first evidence that AgN-DNA species can possess additional chloride ligands that lead to increased stability in biologically relevant concentrations of chloride. Mass spectrometry of five chromatographically isolated near-infrared (NIR)-emissive AgN-DNA species with previously reported X-ray crystal structures determines their molecular formulas to be (DNA)2[Ag16Cl2]8+. Chloride ligands can be exchanged for bromides, which red-shift the optical spectra of these emitters. Density functional theory (DFT) calculations of the 6-electron nanocluster show that the …
A study of VUV emission and the extracted electron-ion ratio in hydrogen and deuterium plasmas of a filament-driven H−/D− ion source
2019
Vacuum ultraviolet (VUV) emission diagnostics for studying differences of electron impact processes in hydrogen and deuterium plasmas are presented. The method is applied to study a filament driven multicusp arc discharge negative ion source by comparing the VUV-emission intensities of different emission bands and extracted currents of H−/D− ions and electrons. It was found that the ratio of coextracted electrons to extracted ions is four times higher for deuterium than for hydrogen. No significant differences of the VUV-spectra or volumetric rates of ionization, excitation, production of high vibrational states, and dissociation were found between the plasmas of the two isotopes. The volum…
Effective Hamiltonians in Nonrelativistic Quantum Electrodynamics
2021
In this paper, we consider some second-order effective Hamiltonians describing the interaction of the quantum electromagnetic field with atoms or molecules in the nonrelativistic limit. Our procedure is valid only for off-energy-shell processes, specifically virtual processes such as those relevant for ground-state energy shifts and dispersion van der Waals and Casimir-Polder interactions, while on-energy-shell processes are excluded. These effective Hamiltonians allow for a considerable simplification of the calculation of radiative energy shifts, dispersion, and Casimir-Polder interactions, including in the presence of boundary conditions. They can also provide clear physical insights int…
The Diversification of Sicilian Farms: A Way to Sustainable Rural Development
2021
Rural areas still suffer from a lack of sustainable development, and the diversification of farms may be a step in the right direction. The paper provides a detailed picture of the diversification of Sicilian farms into tourism services. Specifically, we propose a simple indicator of localization intensity of agritourism farms and explore their spatial distribution at municipality level. Our study highlights that Sicilian farms rarely diversify into tourism services, despite being situated in attractive areas. That said, some significant spatial clusters of municipalities where agritourism farms are highly concentrated do emerge from the study.
Hartree - Fock simulation of the Ag/MgO interface structure
1996
The atomic and electronic structure of the Ag/MgO interface are calculated using an ab initio Hartree - Fock computer code and a supercell model of a silver monolayer atop three layers of MgO substrate. The band structure, electronic density distribution and densities of states are analysed in detail for isolated and interacting slabs of a metal and MgO. The energetically most favoured adsorption position for Ag atoms is found to be above the O atoms, with the binding energy of 0.20 eV and the equilibrium Ag - O distance of 2.64 A. Neither appreciable charge transfer in the interfacial region, nor considerable population of bonds between the silver monolayer and the insulating substrate tak…