Uncoupled Hartree-Fock calculations of the polarizability and hyperpolarizabilities of nitrophenols

The polarizability and hyperpolarizabilities of nitrophenols as model compounds for studying nonlinear optics have been investigated at the Hartree-Fock level of approximation by means of the Dalgarno Uncoupled Hartree-Fock (DUHF) or Sum Over Orbitals (SOO) method. The additive character and the charge transfer effects in α,β,γ and have been analyzed in terms of the δ and π molecular orbital contributions, the contribution of the individual π molecular orbitals, and the contribution of the highest occupied and the lowest unoccupied\ud molecular orbitals. Within the SOO approach, the reliability of the Two-Level Model has been tested and the influence of the rotation of the nitro group and of the presence of the intramolecular hydrogen bonding in ortho-nitrophenol have been studied. The results show that the present method is a reliable and efficient tool for the prediction of trends in the molecular polarizability and hyperpolarizabilities of large molecule

Photoelectron spectra of fluorine substituted diazanaphthalenes: “Even cases”

The high resolution He 584 Å photoelectron spectra of three diazanaphthalenes and some of their fluorine derivatives are presented. The qualitative model that is used frequently in the discussion of lone-pair level splittings is examined

Accommodative esotropia: Efficacy of treatment

Accommodative esotropia: Efficacy of treatmen

Basis set effects on the electron density and spectroscopic properties of CO

The effect of basis set incompleteness on the deformation density of CO is studied by comparing various STO basis sets with a fully numerical (basis-free) result. A triple-zeta s, p basis plus one 3d and one 4f function appears to be practically converged. The convergence characteristics of other properties (Re, De, ωe, μ0, μ1, electric field gradient (EFG)) with respect to basis set size and type are also investigated. The convergence behaviour is similar for these properties and the deformation densities

Verification, Validation and Testing of Kinetic Mechanisms of Hydrogen Combustion in Fluid Dynamic Computations

A one-step, a two-step, an abridged, a skeletal and four detailed kinetic schemes of hydrogen oxidation have been tested. A new skeletal kinetic scheme of hydrogen oxidation has been developed. The CFD calculations were carried out using ANSYS CFX software. Ignition delay times and speeds of flames were derived from the computational results. The computational data obtained using ANSYS CFX and CHEMKIN, and experimental data were compared. The precision, reliability, and range of validity of the kinetic schemes in CFD simulations were estimated. The impact of kinetic scheme on the results of computations was discussed. The relationship between grid spacing, timestep, accuracy, and computational cost were analyzed.Comment: The alternate reference of this paper: V.P. Zhukov, "Verification, Validation and Testing of Kinetic Models of Hydrogen Combustion in Fluid Dynamic Computations", Paper ID35 at 4th European Conference for Aerospace Sciences, Saint Petersburg, Russia, 4--8 July, 201

Synthesis and Thermally and Light Driven Cleavage of an N-Heterocyclic Diphosphine with Inorganic Backbone

A diphosphine with an unsupported PP bond connecting two carbon-free "inorganic" 1,3,2,4,5-diazaphosphadisilolidine rings was prepared by reductive coupling of a P-chloro-substituted monocyclic precursor molecule. VT-EPR studies revealed that the diphosphine exists in solution, like other compounds of this kind, in dynamic equilibrium with the corresponding phosphinyl radicals. Determination of the radical concentration from the EPR spectra permitted to calculate thermochemical parameters for the homolytic PP bond fission. The results disclose that both the enthalpy and entropy of dissociation are higher than in topologically related bi(diazaphospholidines). The impact of the entropy term allows explaining that, regardless of the presence of an energetically rather stable PP bond, the onset of dissociation is observable even at ambient temperature. Irradiation experiments showed that radical formation cannot only be induced thermally, but also by photolysis.Peer reviewe

Reactions of Imidazolio-Phosphides with Organotin Chlorides : Surprisingly Diverse

Reactions of primary imidazolio-phosphides ("imidazolylidene-phosphinidenes") with R2SnCl2 yield as main products spectroscopically detectable Lewis pairs which undergo base-induced dehydrochlorination in the presence of excess dichlorostannane to afford zwitterionic chloride adducts of distannylated imidazolio-phosphines. In contrast, reactions with R3SnCl proceed under dismutation to furnish mixtures containing imidazolium salts and stannylated (oligo)phosphines P(SnR3)(3) and P-7(SnR3)(3), respectively. DFT studies were used to rationalize the divergent behavior based on the presumption that the reactions proceed under thermodynamic control and the products observed represent the most stable species under the specific reaction conditions. Computational simulation of selected reaction steps provides a model mechanism for Lewis-acid promoted creation of PP-bonds, which is a prerequisite for oligophosphine formation. The computational studies further highlight parallels between reactions of imidazolio-phosphides with Lewis and Bronsted acids, and allow also to extrapolate the behavior of the P-nucleophiles towards other electrophiles than organotin chlorides.Peer reviewe

Annellated 1,3,4,2-Triazaphospholenes-Simple Modular Synthesis and a First Exploration of Ligand Properties

The successful use of 1,3,4,2-triazaphospholenes (TAPs) as organo-catalysts stresses the need for efficient synthetic routes to these molecules. In this study, we establish the [1 + 4]-cycloaddition of PBr3 to azo-pyridines as a new approach to preparing pyrido-annellated TAPs in a single step from easily available precursors. The modular assembly of the azo-component via condensation of primary amines and nitroso compounds along with the feasibility of post-functionalization at the P–Br bond under conservation of the heterocyclic structure allows, in principle, to address a wide range of target molecules, which is illustrated by prototypical examples. The successful synthesis of a transition metal complex confirms for the first time the ability of a TAP to act as a P-donor ligand. Crystallographic studies suggest that hyperconjugation effects and intermolecular interactions induce a qualitatively similar ionic polarization of the P–Br bonds in TAPs as in better known isoelectronic diazaphospholenes