Search results for "Localized"
showing 10 items of 297 documents
Microscopic properties of liquid water from combined ab initio molecular dynamics and energy decomposition studies
2013
The application of newly developed first-principle modeling techniques to liquid water deepens our understanding of the microscopic origins of its unusual macroscopic properties and behaviour. Here, we review two novel ab initio computational methods: second-generation Car-Parrinello molecular dynamics and decomposition analysis based on absolutely localized molecular orbitals. We show that these two methods in combination not only enable ab initio molecular dynamics simulations on previously inaccessible time and length scales, but also provide unprecedented insights into the nature of hydrogen bonding between water molecules. We discuss recent applications of these methods to water cluste…
Influence of applied strain on the microstructural corrosion of AlMg2 as-cast aluminium alloy in sodium chloride solution
2012
International audience; The corrosion behavior of ISO AlMg2 (AA5052) was studied at the microscale using the Electrochemical Microcell Technique. The influence of plastic deformation on the corrosion resistance of this alloy was also examined. After polishing, pitting at small copper-enriched precipitates and structural etching were observed. After deformation, numerous slip bands were found in grains. After 5.5% plastic strain, the global electrochemical behavior of samples was significantly affected. Pitting potential was decreased in sites containing slip bands or in sites with large strain gradients (measured using microgauges deposited by lithography).
Periodic models in quantum chemical simulations ofF centers in crystalline metal oxides
2007
We present a survey of recent first principles simulations of the neutral oxygen vacancies (F centers) existing as native or radiation-induced point defects in various crystalline metal oxides in different forms (bulk, bare substrate surface, and on the interface with metal adsorbates). We mainly consider periodic models in calculations of point defects using the metal oxide supercell or cyclic clusters. We compare different formalisms of first principles calculations, mostly the Density Functional Theory (DFT) as implemented in the framework of either localized basis set of atomic orbitals or delocalized basis sets of plane waves. We analyze in detail the structural and electronic properti…
Co-crystallization of atomically precise metal nanoparticles driven by magic atomic and electronic shells
2018
This paper reports co-crystallization of two atomically precise, different-size ligand-stabilized nanoclusters, a spherical (AuAg)267(SR)80 and a smaller trigonal-prismatic (AuAg)45(SR)27(PPh3)6 in 1:1 ratio, characterized fully by X-ray crystallographic analysis (SR = 2,4-SPhMe2). The larger cluster has a four concentric-shell icosahedral structure of Ag@M12@M42@M92@Ag120(SR)80 (M = Au or Ag) with the inner-core M147 icosahedron observed here for metal nanoparticles. The cluster has an open electron shell of 187 delocalized electrons, fully metallic, plasmonic behavior, and a zero HOMO-LUMO energy gap. The smaller cluster has an 18-electron shell closing, a notable HOMO-LUMO energy gap and…
Plasmonic nanostructures for light trapping in thin-film solar cells
2019
Abstract The optical properties of localized surface plasmon resonances (LSPR) sustained by self-assembled silver nanoparticles are of great interest for enhancing light trapping in thin film photovoltaics. First, we report on a systematic investigation of the structural and the optical properties of silver nanostructures fabricated by a solid-state dewetting process on various substrates. Our study allows to identify fabrication conditions in which circular, uniformly spaced nanoparticles are obtainable. The optimized NPs are then integrated into plasmonic back reflector (PBR) structures. Second, we demonstrate a novel procedure, involving a combination of opto-electronic spectroscopic tec…
Ultrastrong Coupling of Plasmons and Excitons in a Nanoshell
2014
The strong coupling regime of hybrid plasmonic-molecular systems is a subject of great interest for its potential to control and engineer light-matter interactions at the nanoscale. Recently, the so-called ultrastrong coupling regime, which is achieved when the light-matter coupling rate reaches a considerable fraction of the emitter transition frequency, has been realized in semiconductor and superconducting systems and in organic molecules embedded in planar microcavities or coupled to surface plasmons. Here we explore the possibility to achieve this regime of light-matter interaction at nanoscale dimensions. We demonstrate by accurate scattering calculations that this regime can be reach…
Hot-Carrier Generation in Plasmonic Nanoparticles: The Importance of Atomic Structure
2020
Metal nanoparticles are attractive for plasmon-enhanced generation of hot carriers, which may be harnessed in photochemical reactions. In this work, we analyze the coherent femtosecond dynamics of photon absorption, plasmon formation, and subsequent hot-carrier generation through plasmon dephasing using first-principles simulations. We predict the energetic and spatial hot-carrier distributions in small metal nanoparticles and show that the distribution of hot electrons is very sensitive to the local structure. Our results show that surface sites exhibit enhanced hot-electron generation in comparison to the bulk of the nanoparticle. While the details of the distribution depend on particle s…
First-principles calculations of the atomic and electronic structure ofFcenters in the bulk and on the (001) surface ofSrTiO3
2006
The atomic and electronic structure, formation energy, and the energy barriers for migration have been calculated for the neutral O vacancy point defect F center in cubic SrTiO3 employing various implementations of density functional theory DFT. Both bulk and TiO2-terminated 001 surface F centers have been considered. Supercells of different shapes containing up to 320 atoms have been employed. The limit of an isolated single oxygen vacancy in the bulk corresponds to a 270-atom supercell, in contrast to commonly used supercells containing 40– 80 atoms. Calculations carried out with the hybrid B3PW functional show that the F center level approaches the conduction band bottom to within 0.5 eV…
Ultrastable, Uniform, Reproducible, and Highly Sensitive Bimetallic Nanoparticles as Reliable Large Scale SERS Substrates
2015
International audience; A strong interest exists in developing surface-enhanced Raman spectroscopy (SERS) substrates that uniformly enhance Raman signals of chemical and biological molecules over large scales while reaching the detection limit of trace concentrations. Even though the resonant excitation of localized surface plasmons of single or assembled metallic nanoparticles used in SERS substrates can induce large electromagnetic fields, these substrates display a SERS activity which suffers from poor reproducibility, uniformity, and stability, preventing them from being reliable for applications. In this work, we have developed self-supported large scale Ag/Au bimetallic SERS-active su…
Hydrogen in metals: Quantum aspects
1984
Hydrogen atoms are usually considered chemisorbed at well-defined sites on surfaces. We advocate a completelydifferent view, and demonstrate that chemisorbed hydrogen exhibits pronounced quantum effects. The hydrogen atom is to a large degree delocalized in both ground and excited-stated configurations: a proper description can only be given in terms of hydrogen energy bands. An analogous picture emerges for hydrogen isotopes (including muon) diffusing interstitially in bulk metals. The ground state there corresponds to a self-trapped situation: a localized impurity with an associated lattice distortion field. A powerful computational scheme is presented, which entails (i) the construction …