Search results for " quantum chemistry"
showing 10 items of 549 documents
Oxidation of pentan-2-ol -Part II: Experimental and modeling study
2021
International audience; The oxidation of pentan-2-ol was investigated at high-pressure in a jet-stirred reactor and in a shock tube. Experiments in the JSR were carried out at 10 atm, between 500-1180 K, for five different equivalence ratios of = 0.35, 0.5, 1, 2, 4 and 1000 ppm of fuel, at a constant residence time of 0.7 s. Reactant, product and intermediate species mole fractions were quantified using Fourier transform infrared spectrometry (FTIR) and gas chromatography (GC). Ignition delay times were measured for pentan-2-ol/O 2 mixtures in argon in a shock tube at 20 and 40 bar, in a temperature range of 1070-1460 K and for equivalence ratios of = 0.5, 1 and 2. Ignition delay times of a…
Metallization of the Na 14 Cl 13 Cluster
1994
The structure and energetics of multiple-excess-electron alkali halide clusters Na14Cl14-n, (1 ≤ n ≤ 6) is studied by ab initio calculations using norm-conserving pseudopotentials and local-spin-density-functional theory. Analysis of various electronic properties (Kohn-Sham one-electron eigenvalue spectra, ionization potentials, participation ratios of Kohn-Sham orbitals), as well as multiple F-center formation energies, suggests that these clusters can be characterized as Nan(NaCl)14-n having a "phase-separated" metallic part NaI. The Na14Cl9 (or Na14Cl9+) cluster exhibits a face (surface) segregated metallic Na5 (Na5+) overlayer, the stability of which is demonstrated by a molecular-dynam…
Ab initiocalculations of theFcenters in MgF2bulk and on the (001) surface
2012
We present and discuss the results of atomic and electronic structure calculations of the F centers in MgF2 bulk and on the (001) surface. The calculations are based on the B3PW Hartree–Fock and density functional theory hybrid exchange-correlation functional. Most of the electronic density of a missing fluorine ion is localized in the bulk vacancy and a little bit less—in a surface vacancy. It is shown that the electronic F center is a deep donor. The lattice distortion and defect formation energy on the neutral (001) surface and in the bulk are also compared.
Impact of point defects on the elastic properties of BaZrO3: Comprehensive insight from experiments and ab initio calculations
2018
Abstract Acceptor doped BaZrO3 is the prototype of proton conducting perovskites which are of strong interest as electrolytes for intermediate temperature fuel cells. Elastic properties of both dry and hydrated Y-doped BaZrO3 (1.5–17 mol% Y) were determined using ultrasound time of flight (TOF) measurements, and complemented by ab initio calculations which allow for an analysis of the different contributions. The experimental and theoretical findings are consistent and reveal a strong decrease of the Young's, shear and bulk moduli upon increasing dopant concentration. This decrease is attributed to a combined effect of (i) macroscopic lattice chemical expansion mainly caused by differing io…
Modulation of the magnetic anisotropy of octahedral cobalt(ii) single-ion magnets by fine-tuning the axial coordination microenvironment
2019
Two mononuclear cobalt(II) complexes, with the formulas [Co(2,6-dfba)2(bpp)2(H2O)2]n (1) and [Co(2,6-dfba)2(bpe)2(H2O)2]n (2) (2,6-Hdfba = 2,6-difluorobenzoic acid, bpp = 1,3-bis(4-pyridyl)propane, bpe = 1,2-bis(4-pyridyl)ethylene), have been synthesized by combining Co(II) ions with benzoate derivatives and two homogeneous N-donor ligands, respectively. Constrained by the analogous CoN2O4 coordination spheres, the discretely hexa-coordinated Co(II) cores in both complexes display stretched octahedral geometries. The equatorial environments in both complexes are identical, whereas the axial sites are finely modulated by the different chemical natures of the terminal N-donor ligands. The com…
First-principles calculations of point defects in inorganic nanotubes
2013
The first-principles calculations have been performed to investigate the ground-state properties of monoperiodic boron nitride (BN), TiO2, and SrTiO3 single-walled nanotubes (SW NTs) containing extrinsic point defects. The hybrid exchange–correlation functionals PBE, B3LYP, and B3PW within the framework of density functional theory (DFT) have been applied for large-scale ab initio calculations on NTs with the following substitutional impurities: AlB, PN, GaB, AsN, InB, and SbN in the BN NT, as well as CO, NO, SO, and FeTi in the TiO2 and SrTiO3 NTs, respectively. The variations in formation energies obtained for equilibrium defective nanostructures allow us to predict the most stable compos…
Optical Contrast and Raman Spectroscopy Techniques Applied to Few-Layer 2D Hexagonal Boron Nitride
2019
The successful integration of few-layer thick hexagonal boron nitride (hBN) into devices based on two-dimensional materials requires fast and non-destructive techniques to quantify their thickness. Optical contrast methods and Raman spectroscopy have been widely used to estimate the thickness of two-dimensional semiconductors and semi-metals. However, they have so far not been applied to two-dimensional insulators. In this work, we demonstrate the ability of optical contrast techniques to estimate the thickness of few-layer hBN on SiO2/Si substrates, which was also measured by atomic force microscopy. Optical contrast of hBN on SiO2/Si substrates exhibits a linear trend with the number of h…
Ab initio LCAO study of the atomic, electronic and magnetic structures and the lattice dynamics of triclinic CuWO4
2013
Abstract The electronic, structural and phonon properties of antiferromagnetic triclinic CuWO 4 have been studied using the first-principles spin-polarized linear combination of atomic orbital (LCAO) calculations based on the hybrid exchange–correlation density functional (DFT)/Hartree–Fock (HF) scheme. In addition, the local atomic structure around both Cu and W atoms has been probed using extended X-ray absorption fine structure (EXAFS) spectroscopy. We show that, by using the hybrid DFT–HF functional, one can accurately and simultaneously describe the atomic structure (the unit cell parameters and the atomic fractional coordinates), the band gap and the phonon frequencies. In agreement w…
Ab initio calculations of indium arsenide in the wurtzite phase: structural, electronic and optical properties
2013
Most III-V semiconductors, which acquire the zinc-blende phase as bulk materials, adopt the metastable wurtzite phase when grown in the form of nanowires. These are new semiconductors with new optical properties, in particular, a different electronic band gap when compared with that grown in the zinc-blende phase. The electronic gap of wurtzite InAs at the Gamma-point of the Brillouin zone (E0 gap) has been recently measured, E0 = 0.46 eV at low temperature. The electronic gap at the A point of the Brillouin zone (equivalent to the L point in the zinc-blende structure, E1) has also been obtained recently based on a resonant Raman scattering experiment. In this work, we calculate the band st…
Ab initio study of the SrTiO3, BaTiO3 and PbTiO3 (001) surfaces
2004
The results of first-principles calculations of the two possible terminations of (0 0 1) surfaces of SrTiO 3 (STO), BaTiO3 (BTO) and PbTiO3 (PTO) perovskites are presented. Surface atomic structures and their electronic configurations have been calculated using ab initio density functional theory (DFT) combined with hybrid (B3PW) exchange-correlation technique. Our results are compared with previous quantum mechanical calculations and available experimental data. Surface relaxations and the electronic states near valence band gap are discussed in details for all three perovskites. © 2004 Elsevier Ltd and Techna Group S.r.l. All rights reserved.