Search results for "init"
showing 10 items of 6629 documents
Study of the electronic and atomic structure of thermally treated SrTiO3(110) surfaces
2003
The electronic structure of heated SrTiO3(110) surfaces was investigated with metastable impact electron spectroscopy and ultraviolet photoelectron spectroscopy (He(I). Scanning tunnelling microscopy and atomic force microscopy (AFM) were used to study the topology of the surface. The crystals were heated up to 1000 °C under reducing conditions in ultrahigh vacuum or under oxidizing conditions in synthetic air for 1 h, respectively. Under both conditions microfacetting of the surface is observed. The experimental results are compared with ab initio Hartree-Fock calculations, also presented here, carried out for both ideal and reconstructed SrTiO 3(110) surfaces. The results give direct evid…
Modeling of defects and surfaces in perovskite ferroelectrics
2002
The results of electronic structure calculations for different terminations of SrTiO3 (100) and (110) perovskite thin films are discussed. These calculations are based on the ab initio Hartree-Fock (HF) method and Density Functional Theory (DFT). Results are compared with previous ab initio plane-wave LDA and classical Shell Model (SM) calculations. Calculated considerable increase of the Ti – O chemical bond covalency nearby the surface is confirmed by experimental data. Our quantum chemical calculations performed by means of the intermediate neglect of differential overlap (INDO) method confirm the existence of self-trapped electrons in KNbO3, KTaO3 and BaTiO3 crystals. The relevant latti…
Coupling between bulk- and surface chemistry in suspensions of charged colloids
2013
The ionic composition and pair correlations in fluid phases of realistically salt-free charged colloidal sphere suspensions are calculated in the primitive model. We obtain the number densities of all ionic species in suspension, including low-molecular weight microions, and colloidal macroions with acidic surface groups, from a self-consistent solution of a coupled physicochemical set of nonlinear algebraic equations and non-mean-field liquid integral equations. Here, we study suspensions of colloidal spheres with sulfonate or silanol surface groups, suspended in demineralized water that is saturated with carbon dioxide under standard atmosphere. The only input required for our theoretical…
Theoretical study of the NH tautomerism in free base porphyrin
1997
Abstract The NH tautomerism of free base porphyrin is investigated at the semiempirical spin-unrestricted AM1 (UAM1) and ab initio RHF/3-21G levels. The UAM1 method provides delocalized geometries for all stationary structures without imposing any symmetry constraint. RHF/3-21G geometry optimizations have to be performed under symmetry restrictions to ensure that realistic delocalized structures are obtained. Both the semiempirical and the ab initio calculations predict that the interconversion between trans tautomers proceeds in an asynchronous two-step process via intermediate cis tautomers. The cis tautomers are characterized as minima in the potential energy surface and are 8–10 kcal m…
InBO3 and ScBO3 at high pressures: an ab initio study of elastic and thermodynamic properties
2016
We have theoretically investigated the elastic properties of calcite-type orthoborates ABO(3) (A= Sc and In) at high pressure by means of ab initio total-energy calculations. From the elastic stiffness coefficients, we have obtained the elastic moduli (B, G and E), Poisson's ratio (nu), B/G ratio, universal elastic anisotropy index (A(U)), Vickers hardness, and sound wave velocities for both orthoborates. Our simulations show that both borates are more resistive to volume compression than to shear deformation (B > G). Both compounds are ductile and become more ductile, with an increasing elastic anisotropy, as pressure increases. We have also calculated some thermodynamic properties, like D…
The Coordination of Uranyl in Water: A Combined Quantum Chemical and Molecular Simulation Study
2005
The coordination environment of uranyl in water has been studied using a combined quantum mechanical and molecular dynamics approach. Multiconfigurational wave function calculations have been performed to generate pair potentials between uranyl and water. The quantum chemically determined energies have been used to fit parameters in a polarizable force field with an added charge transfer term. Molecular dynamics simulations have been performed for the uranyl ion and up to 400 water molecules. The results show a uranyl ion with five water molecules coordinated in the equatorial plane. The U-O(H(2)O) distance is 2.40 A, which is close to the experimental estimates. A second coordination shell…
Dynamic Magnetic and Optical Insight into a High Performance Pentagonal Bipyramidal Dy(III) Single-Ion Magnet
2017
The pentagonal bipyramidal single-ion magnets (SIMs) are among the most attractive prototypes of high-performance single-molecule magnets (SMMs). Here, a fluorescence-active phosphine oxide ligand CyPh2PO (=cyclohexyl(diphenyl)phosphine oxide) was introduced into [Dy(CyPh2PO)2(H2O)5]Br3⋅2 (CyPh2PO)⋅EtOH⋅3 H2O, and combined dynamic magnetic measurement, optical characterization, ab initio calculation, and magneto-optical correlation of this high-performance pseudo-D5h DyIII SIM with large Ueff (508(2) K) and high magnetic hysteresis temperature (19 K) were performed. This work provides a deeper insight into the rational design of promising molecular magnets.
Crystal structure of sinhalite MgAlBO4 under high pressure
2015
We report on high-pressure angle-dispersive X-ray diffraction data up to 27 GPa for natural MgAlBO4 sinhalite mineral and ab initio total energy calculations. The experimental bulk modulus of sinhalite is B-0 = 171(3) GPa with a first-pressure derivative of B-0' = 4.2(3). A comparison with other olivine-type compounds shows that the value for B0 is 27% larger than that of Mg2SiO4 forsterite and 29% smaller than that of Al2BeO4 chrysoberyl. These differences are interpreted, on the basis of our ab initio calculations, in terms of the relative incompressibility of Al-O bonds in AlO6 octahedra (with a calculated bulk modulus of 250(1) GPa) as compared to Mg-O bonds in MgO6 octahedra (with a ca…
Ab Initio Study on the Mechanism of the Reactions of the Nitrate Radical with Haloalkenes: 1,2-Dichloroethene, 1,1-Dichloroethene, Trichloroethene, …
2000
A general mechanism for the reactions of the NO3 radical with 1,2-dichloroethene, 1,1-dichloroethene, trichloroethene, and tetrachloroethene is proposed from ab initio DFT calculations. The calculated mechanism shows three main parallel reaction pathways. For the systems where the two carbon atoms are differently substituted, the study includes both the attacks with Markownikoff and contra-Markownikoff orientation. The first reaction pathway leads to the formation of an epoxide along with the NO2 radical, the second one to the formation of carbonyl compounds, and the third one leads, through the cleavage of the C−C bond, to the formation of carbonyl compounds with a lower number of carbon a…
Principal Poincar\'e Pontryagin Function associated to some families of Morse real polynomials
2014
It is known that the Principal Poincar\'e Pontryagin Function is generically an Abelian integral. We give a sufficient condition on monodromy to ensure that it is an Abelian integral also in non generic cases. In non generic cases it is an iterated integral. Uribe [17, 18] gives in a special case a precise description of the Principal Poincar\'e Pontryagin Function, an iterated integral of length at most 2, involving logarithmic functions with only one ramification at a point at infinity. We extend this result to some non isodromic families of real Morse polynomials.