Search results for "localize"
showing 10 items of 300 documents
Multistate active spaces from local CAS-SCF molecular orbitals: the photodissociation of HFCO as an example.
2005
A recently developed algorithm to generate localized molecular orbitals (LMO) is applied to the study of excited states along a photodissociation process. The LMOs allow for the selection of a consistent complete active space (CAS) for the simultaneous description of all the electronic states involved in a multistate process on the basis of simple chemical criteria. The local nature of the orbitals is used to label them in a unique way that does not depend on the molecular geometry. The selection of the electronic configurations of interest for the set of target states on only the basis of the dominant excitations required by the simplest configuration interaction (CI) descriptions for both…
Evidence of delocalized excitons in amorphous solids
2010
We studied the temperature dependence of the absorption coefficient of amorphous ${\mathrm{SiO}}_{2}$ in the range from 8 to 17.5 eV obtained by Kramers-Kronig dispersion analysis of reflectivity spectra. We demonstrate the main excitonic resonance at 10.4 eV to feature a close Lorentzian shape redshifting with increasing temperature. This provides a strong evidence of excitons being delocalized notwithstanding the structural disorder intrinsic to amorphous ${\mathrm{SiO}}_{2}$. Excitons turn out to be coupled to an average phonon mode of 83 meV energy.
Fragmentation of gold clusters stored in a penning trap
1994
The collision-induced dissociation of positively charged gold clusters (2 to 23 atoms) stored in a Penning trap has been studied. After collisions with rare gases, excited clusters predominantly decay by emission of one or two atoms. The loss of two atoms occurs most likely through the emission of a dimer rather than a sequential evaporation. The minimum kinetic energies of clusters required to induce dissociation exhibit a pronounced odd-even effect. Clusters with an even number of delocalized electrons are more stable than the odd ones.
Experimental and theoretical investigation of Cr1-xScxN solid solutions for thermoelectrics
2016
The ScN- and CrN-based transition-metal nitrides have recently emerged as a novel and unexpected class of materials for thermoelectrics. These materials constitute well-defined model systems for investigating mixing thermodynamics, phase stability, and band structure aiming for property tailoring. Here, we demonstrate an approach to tailor their thermoelectric properties by solid solutions. The trends in mixing thermodynamics and densities-of-states (DOS) of rocksalt-Cr1-xScxN solid solutions (0 ≤ x ≤ 1) are investigated by first-principles calculations, and Cr1-xScxN thin films are synthesized by magnetron sputtering. Pure CrN exhibits a high power factor, 1.7 × 10−3 W m−1 K−2 at 720 K, en…
Magnetic Exchange between Orbitally Degenerate Metal Ions: The Problem of Magnetic Anisotropy
2001
Abstract In this paper we show that a strong magnetic anisotropy appears in exchange mixed–valence clusters containing orbitally degenerate metal ions. Combining an effective Hamiltonian approach with the technique of the irreducible tensor operators (ITO) and pseudoangular momentum representation we have solved the problem of magnetic exchange in localized and delocalized (mixed–valence) systems with different overall symmetries ( D 2 h , D 3 h , D 4 h ). The energy pattern as well as the character of the magnetic anisotropy is closely related to the ground term of the ions, electron transfer pathways, and overall symmetry of the system being affected also by the local crystal fields, spin…
Contribution to the study of physico-chemical properties of surfaces modified by last treatment : application to the enhancement of localized corrosi…
2011
Metallic materials are more and more used in severe conditions with particularly strong request for improving their behavior in aggressive environment and especially over long periods. The objective of this PhD work is to estimate the potentiality of a laser surface melting treatment on the improvement of the stainless steel 304L corrosion resistance, surface treatments by laser can be revisited on the basis of a recent change in the laser technology. In the frame of this work, a nano-pulsed laser fiber was chosen : it allows the treated surface to be melted for few microns in depth, followed by an ultra-fast solidification occuring with cooling rates up to 1011 K/s. The combination of thes…
Evidence for Photoinduced Hole Coupling in BaTiO3:Co
1995
A possible photoinduced correlation mechanism in BaTiO 3 : Co is described. The underlying microscopic process is a local hole photoinjection at a Co 3+ site close to a preexisting metastable hole, The Jahn-Teller field at the Co 2+ site transfers this pair of holes in the next cell along the rhombic direction [111] before normal polaronic or band conduction. The spatial extension of this correlation depends on a characteristic «delocalization» length. This unstable conductive state appears to be possibly frozen in a permanent way below T c
Synthesis, spectroscopic and conformational analysis of 1,4-dihydroisonicotinic acid derivatives
2014
Abstract Structural and conformational properties of 1,4-dihydroisonicotinic acid derivatives, characterized by ester, ketone or cyano functions at positions 3 and 5 in solid and liquid states have been investigated by X-ray analysis and nuclear magnetic resonance and supported by quantum chemical calculations. The dihydropyridine ring in each of the compounds exists in flattened boat-type conformation. The observed ring distortions around the C(4) and N(1) atoms are interrelated. The substituent at N(1) has great influence on nitrogen atom pyramidality. The 1H, 13C and 15N NMR chemical shifts and coupling constants are discussed in terms of their relationship to structural features such as…
First-principles and semiempirical calculations forFcenters inKNbO3
1997
The linear muffin-tin-orbital method combined with density functional theory (local approximation) and the semiempirical method of the intermediate neglect of the differential overlap (INDO) based on the Hartree-Fock formalism are used for the study of the $F$ centers (O vacancy with two electrons) in cubic and orthorhombic ferroelectric KNbO$_3$ crystals. Calculations for 39-atom supercells show that the two electrons are considerably delocalized even in the ground state of the defect. Their wave functions extend over the two Nb atoms closest to the O vacancy and over other nearby atoms. Thus, the $F$ center in KNbO$_3$ resembles electron defects in the partially-covalent SiO$_2$ crystal (…
Valence-Delocalized and Valence-Trapped FeIIFeIII Complexes: Drastic Influence of the Ligands
1997
The two macrocyclic ligands H 2 L 1 and H 2 L 2 are not very different, but their Fe II Fe III complexes are remarkably so. [L 1 Fe 2 (μ-OAc) 2 ](ClO 4 ) is valence-delocalized on the Mossbauer time scale over the range 1.8-364 K, whereas [L 2 Fe 2 (μ-OAc)(OAc)(H 2 O)](ClO 4 )·2H 2 O is valence-trapped even at room temperature. The difference in properties of these complexes is also reflected in their electronic spectra, in their electrochemical and magnetic behavior, and in their structures.