Search results for "SCF"
showing 10 items of 40 documents
Electronic excited states of conjugated cyclic ketones and thioketones : A theoretical study
2002
Absorption spectra of a series of cyclic conjugated ketones and thioketones have been computed at the multiconfigurational second-order multistate perturbation level of theory, the CASSCF/MS-CASPT2 method. Excitation energies, transition dipole moments, oscillator strengths, and static dipole moments are reported and discussed for excited states with energies lower than ≈ 7–8 eV. The main bands of the spectra have been assigned and characterized in most cases for the first time. The spectroscopy of the different systems is compared in detail. Thioketones in particular have low-energy and intense ππ∗ transitions which suggest corresponding enhanced nonlinear molecular optical properties. Add…
The Effect of Ni Doping on the Performance and Electronic Structure of LSCF Cathodes Used for IT-SOFCs
2018
We investigated the effect of nickel doping on the electronic structure and performance of nanostructured La0.6Sr0.4Co0.2Fe0.8-0.03Ni0.03O3-delta prepared by the one-pot sol gel method. The commercial undoped La0.6Sr0.4Co0.2Fe0.8O3-delta (ISCF0.8) was used as reference. Moreover, for comparison, Ni (3 mol %) was deposited by wetness impregnation over the La0.6Sr0.4Co0.2Fe0.8O3-delta. We show by in situ X-ray absorption spectroscopy at 900 degrees C under air flow that nickel enters the B perovskite site of the material and favors the stabilization of the cobalt oxidation state, as evidenced by the delay in the decrease of the average Co valence with respect to undoped samples. Our results a…
Linear and nonlinear optical properties of some organoxenon derivatives
2007
We employ a series of state-of-the-art computational techniques to study the effect of inserting one or more Xe atoms in HC2H and HC4H, on the linear and nonlinear optical (L&NLO) properties of the resulting compounds. It has been found that the inserted Xe has a great effect on the L&NLO properties of the organoxenon derivatives. We analyze the bonding in HXeC2H, and the change of the electronic structure, which is induced by inserting Xe, in order to rationalize the observed extraordinary L&NLO properties. The derivatives, which are of interest in this work, have been synthesized in a Xe matrix. Thus the effect of the local field (LF), due to the Xe environment, on the properties of HXeC2…
Kit Is Expressed by Epithelial Cells In Vivo
2003
In mammalian skin, stem cell factor (SCF) regulates the proliferation and maturation of mast cells and melanocytes, which are thought to be the only cutaneous cells that express the Kit-tyrosine kinase receptor (Kit) and respond to epithelial and mesenchymal-derived SCF. We previously had noted, however, the presence of Kit+ cells in murine hair follicles, in an introepithelial tissue compartment devoid of melanocytes and mast cells. Here we have identified the nature of this Kit+ population of cells in hair follicles of C57BL/6 mice. Anagen hair follicles showed strong Kit immunoreactivity not only in the pigmentary unit above the follicular dermal papilla but also in a much more proximall…
Palladium local structure of La1-xSrxCo1-yFey-0.03Pd0.03O3-δperovskites synthesized using a one pot citrate method
2014
Nanostructured La1-xSrxCo1-yFey-0.03Pd0.03O3-δ(LSCF-Pd) perovskites with fixed La-Sr composition (x = 0.4) and two different Fe contents (y = 0.2 and 0.8) were successfully synthesized using a one pot citrate method starting from nitrates of the metal cations. Pd-free La1-xSrxCo1-yFeyO3-δ(LSCF) systems were prepared for comparison. LSCF powders were calcined at 1300 °C and characterized by XRD and Rietveld refinement, EXAFS, XPS, TPR analyses. Promotion of La0.6Sr0.4Co0.8Fe0.2O3-δand of La0.6Sr0.4Co0.2Fe0.8O3-δby incorporation of palladium was evidenced by solving the local environment of Pd using EXAFS spectroscopy. XPS analyses, in agreement with TPR measurements, demonstrated an inc…
Accurate ab initio density fitting for multiconfigurational self-consistent field methods
2008
Using Cholesky decomposition and density fitting to approximate the electron repulsion integrals, an implementation of the complete active space self-consistent field (CASSCF) method suitable for large-scale applications is presented. Sample calculations on benzene, diaquo-tetra- μ -acetato-dicopper(II), and diuraniumendofullerene demonstrate that the Cholesky and density fitting approximations allow larger basis sets and larger systems to be treated at the CASSCF level of theory with controllable accuracy. While strict error control is an inherent property of the Cholesky approximation, errors arising from the density fitting approach are managed by using a recently proposed class of auxi…
Method specific Cholesky decomposition : Coulomb and exchange energies
2008
We present a novel approach to the calculation of the Coulomb and exchange contributions to the total electronic energy in self consistent field and density functional theory. The numerical procedure is based on the Cholesky decomposition and involves decomposition of specific Hadamard product matrices that enter the energy expression. In this way, we determine an auxiliary basis and obtain a dramatic reduction in size as compared to the resolution of identity (RI) method. Although the auxiliary basis is determined from the energy expression, we have complete control of the errors in the gradient or Fock matrix. Another important advantage of this method specific Cholesky decomposition is t…
The impact of liquid-pressurized extracts of Spirulina, Chlorella and Phaedactylum tricornutum on in vitro antioxidant, antiinflammatory and bacteria…
2022
The impact of Spirulina, Chlorella and Phaeodactylum tricornutum (P. tricornutum) microalgal extracts obtained by pressurized liquid extraction (PLE) on antioxidant and anti-inflammatory activities, microbial growth and in vitro gut microbiota composition was evaluated. PLE, compared to conventional extraction, led to a significant (p < 0.05) increase in proteins, carbohydrates, polyphenols, and antioxidant capacities of the three microalgal extracts. Moreover, Spirulina and P. tricornutum extracts significantly (p < 0.05) reduced the in vitro activation of the inflammatory NF-κB pathway. The microalgal extracts had also an inhibitory effect on the pathogenic bacteria while potential benefi…
Computation of conical intersections by using perturbation techniques
2005
Multiconfigurational second-order perturbation theory, both in its single-state multiconfigurational second-order perturbation theory (CASPT2) and multistate (MS-CASPT2) formulations, is used to search for minima on the crossing seams between different potential energy hypersurfaces of electronic states in several molecular systems. The performance of the procedures is tested and discussed, focusing on the problem of the nonorthogonality of the single-state perturbative solutions. In different cases the obtained structures and energy differences are compared with available complete active space self-consistent field and multireference configuration interaction solutions. Calculations on dif…
Multiconfigurational second-order perturbation study of the decomposition of the radical anion of nitromethane
2004
The doublet potential energy surfaces involved in the decomposition of the nitromethane radical anion (CH(3)NO(2) (-)) have been studied by using the multistate extension of the multiconfigurational second-order perturbation method (MS-CASPT2) in conjunction with large atomic natural orbital-type basis sets. A very low energy barrier is found for the decomposition reaction: CH(3)NO(2) (-)--[CH(3)NO(2)](-)--CH(3)+NO(2) (-). No evidence has been obtained on the existence of an isomerization channel leading to the initial formation of the methylnitrite anion (CH(3)ONO(-)) which, in a subsequent reaction, would yield nitric oxide (NO). In contrast, it is suggested that NO is formed through the …