Search results for "Density"
showing 10 items of 4402 documents
Absolute acidity of clay edge sites from ab-initio simulations
2012
International audience; We provide a microscopic understanding of the solvation structure and reactivity of the edges of neutral clays. In particular we address the tendency to deprotonation of the different reactive groups on the (0 1 0) face of pyrophyllite. Such information cannot be inferred directly from titration experiments, which do not discriminate between different sites and whose interpretation resorts to macroscopic models. The determination of the corresponding pKa then usually relies on bond valence models, sometimes improved by incorporating some structural information from ab-initio simulations. Here we use density functional theory based molecular dynamics simulations, comb…
Diferrocenyl oligothiophene wires: Raman and quantum chemical study of valence-trapped cations
2011
A combination of Raman spectroscopy and density functional theory calculations is used to describe the structural and spectroscopic properties of the different isomeric cations of diferrocenyl quaterthiophenes. Isomerisation of the thienyl β-positions provides site selective oxidation, which gives rise to species that can interconvert by moving the charge over the bridge. The spectroscopic study allows us to describe a sequence of stationary trapped cationic, either ferrocenyl or thienyl, states which constitutes an energy cascade of accessible sites through which the charge transfer can proceed.
Valence instabilities and inhomogeneous mixed valence in some ternary europium compounds
1997
Abstract Photoemission spectra and TB-LMTO-ASA band structure calculations of some mixed valency europium compounds hve been studied. The band structures are compared with the band structures of the isostructural lanthanum and strontium compounds. Surprisingly a 4f density of states in the vicinity of the Fermi level is observed in inhomogenous mixed valency EuPd 3 B, Eu 3 S 4 , and EuPdP. Indeed a van Hove Singularity (vHS) derived from the d states of La and Pd or p states of boron or phosphorous are found in La 3 S 4 , LaPd 3 B and SrPdP. The valence instability in the Eu compounds is thus not necessarily due to Eu 4f states. The results also provide some ground for the assumption that i…
Theoretical calculations on the valence electronic structure of naphthalocyanine: comparison with experimental photoemission data
1993
Abstract We present a theoretical investigation of the electronic structure of metal-free 2,3-naphthalocyanine (2,3-H2Nc) using the valence effective Hamiltonian (VEH) technique. The VEH-DOVS curves obtained for 2,3-H2Nc are correlated with those calculated for naphthalene molecule and a one-to-one correspondence is found. From the electronic structure standpoint, naphthalocyanine has to be viewed as formed by joining four naphthalene moieties to the central carbon-nitrogen ring. An excellent quantitative agreement is found between VEH-DOVS curves and experimental photoemission data.
First-principles calculations of surfaceHcenters inBaF2
2010
H center, a hole trapped at an interstitial anion site, placed on the 111 surface of Barium fluoride BaF2 has been studied by using density functional theory DFT with hybrid exchange potentials, namely, DFT-B3PW. Two different configurations of surface H center are investigated carefully. Both surface H-center systems have strong relaxations because of the surface effect. In the configuration that the interstitial fluorine atom is within the surface, named case 1 in this paper, the unpaired electron is almost equally distributed onto the two atoms of the H center, which is quite different from the bulk H-center case. The other configuration with one of the F atoms of the H center located ab…
Ground state properties of SmB6
2002
Abstract We have studied the ground state properties of the intermediate valence narrow-gap semiconductor SmB 6 by means of point-contact (PC) spectroscopy and specific heat measurements. The density of states derived from PC tunneling spectra could be decomposed into two energy-dependent parts with E g =21 meV and E d =4.5 meV wide gaps, and a finite residual density of states at the Fermi level. The specific heat of SmB 6 is enhanced below about 2 K, more pronounced for the sample with less impurities. This behavior can be attributed to the formation of a coherent state within the residual density of states in the energy gap.
Valence-band electronic structure of CdO, ZnO, and MgO from x-ray photoemission spectroscopy and quasi-particle-corrected density-functional theory c…
2009
The valence-band density of states of single-crystalline rock-salt CdO(001), wurtzite $c$-plane ZnO, and rock- salt MgO(001) are investigated by high-resolution x-ray photoemission spectroscopy. A classic two-peak structure is observed in the VB-DOS due to the anion $2p$-dominated valence bands. Good agreement is found between the experimental results and quasi-particle-corrected density-functional theory calculations. Occupied shallow semicore $d$ levels are observed in CdO and ZnO. While these exhibit similar spectral features to the calculations, they occur at slightly higher binding energies, determined as 8.8 eV and 7.3 eV below the valence band maximum in CdO and ZnO, respectively. Th…
Electronic structure of large disc-type donors and acceptors
2010
Searching for new pi-conjugated charge-transfer systems, the electronic structure of a new acceptor-donor pair derived from coronene (C(24)H(12)) was investigated by ultraviolet photoelectron spectroscopy (UPS). The acceptor coronene-hexaone (C(24)H(6)O(6), in the following abbreviated as COHON) and the donor hexamethoxycoronene (C(30)H(24)O(6), abbreviated as HMC) were adsorbed as pure and mixed phases on gold substrates. At low coverage, COHON adsorption leads to the appearance of a charge-transfer induced interface state 1.75 eV below the Fermi energy. At multilayer coverage the photoemission intensity of the interface state drops and the valence spectrum of neutral COHON appears. The sa…
Iso-valence Co(II) and mixed-valence Co(II/III) tetranuclear complexes: Synthesis, structure, magnetic properties and DFT study
2013
Abstract The reaction of Co(ClO4)2·6H2O with symmetrical N4O3 coordinating heptadentate ligand (H3L) in presence of triethylamine yielded cobalt(II) tetranuclear complexes [Co4(L)2](ClO4)2, 1. When the same reaction is carried out with sodium azide instead of triethylamine afforded tetranuclear mixed-valence Co(II/III) species, [Co4(L)2(μ1,3–N3)2](ClO4)2, 2. Here L3− is the deprotonated form of 2,6-bis[{{(1-hydroxy-2-methylpropan-2-yl)(pyridine-2-ylmethyl)}amino}methyl]-4-methylphenol. Complex 1 crystallizes in the cubic system, space group Fd-3c, with unit-cell parameters a = b = c = 43.320(5) A, Z = 48, whereas complex 2 crystallizes in the space group I41/a in the tetragonal crystal syst…
Nonstationary response envelope probability densities of nonlinear oscillators
2006
The nonstationary random response of a class of lightly damped nonlinear oscillators subjected to Gaussian white noise is considered. An approximate analytical method for determining the response envelope statistics is presented. Within the framework of stochastic averaging, the procedure relies on the Markovian modeling of the response envelope process through the definition of an equivalent linear system with response-dependent parameters. An approximate solution of the associated Fokker-Planck equation is derived by resorting to a Galerkin scheme. Specifically, the nonstationary probability density function of the response envelope is expressed as the sum of a time-dependent Rayleigh dis…