Search results for "ORBIT"
showing 10 items of 1104 documents
X-X through-cage bonding in Cu, Ni, and Cr complexes with M3X2 cores (X=S, As).
2008
Density functional calculations on trinuclear complexes bridged by two sulfur atoms, [(tmeda)(3)Cu(3)(mu-S)(2)](3+), [(tmeda)(3)Ni(3)(mu-S)(2)](2+), and [(tmeda)(3)Ni(3)(mu-S(2))](4+), as well as on the formation of [(tmeda)(3)Cu(3)(mu-S)(2)](3+) from a dinuclear [(tmeda)(2)Cu(2)(mu-S(2))](2+) complex and a mononuclear [(tmeda)Cu(eta(2)-S(2))](+) fragment, are reported. A qualitative orbital analysis of the M(3)X(2) framework bonding is presented for the case in which each metal atom M has a square planar coordination sphere completed by one bidentate or two monodentate ligands (that is, [(L(2)M)(3)X(2)] compounds). It is concluded that a framework electron count (FEC) of 12 corresponds to …
[1,2,3]Triazolo[1,5-a]pyridines. A theoretical (DFT) study of the ring-chain isomerization
2008
The ring opening isomerization of [1,2,3]triazolo[1,5-a]pyridines to the corresponding 2-pyridyl derivatives has been studied by means of DFT calculations at the B3LYP/6-31+G(d,p) computational level. The effect of the substitution as well as those of protonation, deprotonation, and lithiation on different positions has been studied. The electronic characteristics of the optimized structures have been analyzed by means of the Atoms In Molecules (AIM), Electron Localization Function (ELF), Molecular Electrostatic Potential (MEP), and Natural Bond Orbital (NBO) methodologies. © 2008 Elsevier Ltd. All rights reserved.
Ultrahigh-Resolution Mass Spectrometry in Real Time: Atmospheric Pressure Chemical Ionization Orbitrap Mass Spectrometry of Atmospheric Organic Aeros…
2018
The accurate and precise mass spectrometric measurement of organic compounds in atmospheric aerosol particles is a challenging task that requires analytical developments and adaptations of existing techniques for the atmospheric application. Here we describe the development and characterization of an atmospheric pressure chemical ionization Orbitrap mass spectrometer (APCI-Orbitrap-MS) for the measurement of organic aerosol in real time. APCI is a well-known ionization technique, featuring minimal fragmentation and matrix dependencies, and allows rapid alternation between the positive and negative ionization mode. As a proof of principle, we report ambient organic aerosol composition in rea…
Direct analysis in real-time high-resolution mass spectrometry as a valuable tool for polyphenols profiling in olive oil
2018
A fast and reliable method to characterize the polyphenolic compound profiles in extra virgin olive oil (EVOO) has been developed using direct analysis in real time (DART) and linear ion-trap Orbitrap mass spectrometry (LTQ-Orbitrap-MS). Hydroalcoholic extraction increased speed and reduced matrix effects, and DART-MS/MS ensured accurate analysis. Characterization of polyphenol fingerprinting in EVOO samples takes 2 min. This method exhibited proper linearity (R2 ≥ 0.99) in the range of 5–2500 μg g−1, limit of detection (LOD) of 1.5 μg g−1 (signal-to noise S/N = 3), and limits of quantitation (LOQs) of 5 μg g−1 (S/N = 10) for resveratrol (a polyphenol not detected in olive oil). Six spiked …
Selected dissociation‐ and correlation‐consistent configuration interaction by a perturbative criterion
1990
We propose a perturbative criterion to select the most important dissociation‐ or correlation‐consistent type of contributions to perform generalized valence bond‐configuration interaction (GVB‐CI) calculations, dissociation‐consistent configuration interaction (DCCI) or correlation‐consistent configuration interaction (CCCI) approach, respectively. The procedure presented is computationally less demanding than the CCCI proposed by Goddard and co‐workers. To ensure the distance consistency of the MOs used, the nonvalence virtual orbitals are obtained by a projection technique. The results obtained for a few test calculations show the ability of the suggested approach to get close results to…
Proposal of a new diffractive corneal inlay to improve near vision in a presbyopic eye
2020
[EN] A new class of diffraction-based corneal inlays for treatment of presbyopia is described. The inlay is intended to achieve an improvement of the near focus quality over previous designs. Our proposal is a two-zone hybrid device with separated amplitude and phase areas having a central aperture and no refractive power. An array of micro-holes is distributed on the surface of the inlay conforming a binary photon sieve. In this way, the central hole of the disk contributes to the zero order of diffraction, and the light diffracted by the micro-holes in the peripheral photon sieve produces a real focus for near vision. We employed ray-tracing software to study the performance of the new in…
Mechanism of photoluminescence in intrinsically disordered CaZrO3 crystals: First principles modeling of the excited electronic states
2017
Abstract CaZrO3 (CZO) powders obtained by the polymeric precursor method at 400 °C, and then, the samples were annealed at different temperatures (400, 600, 800, and 1000 °C) and characterized by X-ray diffraction, Raman and ultraviolet–visible spectroscopic methods, along with photoluminescence (PL) emissions. First principle calculations based on the density functional theory (DFT), using a periodic cell models, provide a theoretical framework for understanding the PL spectra based on the localization and characterization of the ground and electronic excited states. Fundamental (singlet, s ) and excited (singlet, s* , and triplet, t* ) electronic states were localized and characterized us…
Electrochemical reduction properties of A-frame compounds and crystal structure of Pd2(dppm)2(Me)2(Br)+ dimer
2006
Abstract Two series of A-frame complexes, [Pd2(dppm)2(R)2(μ-X)]+ (R = Me and X = Cl, Br, I, H; R = Mes and X = Br, I), were investigated by cyclic voltammetry (CV). The 2-electron reduction potentials for the first series increase from I (−1.10), Br (−1.17), Cl (−1.25) to H (−1.65 V versus SCE, in CHCl3), as well as in the second series; Br (−1.35) and I (−1.38 V versus SCE, in THF). The nature of the LUMO where the electron reduction takes place is qualitatively addressed by DFT on the corresponding model complexes [Pd2(H2PCH2PH2)2(R)2(μ-X)]+. The LUMO and (LUMO + 1) of the halide derivatives exhibit the presence of Pd d x 2 - y 2 atomic orbitals interacting in an anti-bonding fashion with…
Syndrome de la fissure orbitaire supérieure post-traumatique : mise au point
2016
The traumatic superior orbital fissure syndrome is an uncommon complication of craniomaxillofacial trauma. The diagnosis is clinical and associates ophtalmoplegia (constantly at initial clinical examination), ptosis and anaesthesia of the forehead. Young men victim of road traffic accidents are most often affected. CT-scan usually shows facial and/or craniofacial fractures more or less spreading towards the superior orbital fissure. The absence of fracture seen at the X-rays does not eliminate the diagnosis. Initial management should be multidisciplinary (maxillofacial surgeons, ophthalmologists and neurosurgeons) and conducted early if possible. It combines high-dose corticosteroids and de…
Positive solutions of Dirichlet and homoclinic type for a class of singular equations
2018
Abstract We study a nonlinear singular boundary value problem and prove that, depending on a relationship between exponents of power terms, the problem has either solutions of Dirichlet type or homoclinic solutions. We make use of shooting techniques and lower and upper solutions.