Theoretical investigation of the sulphur K-LL auger energies and chemical shifts in a series of sulphur compounds

Two series of investigations are reported on LL double-hole states of molecules containing sulphur. First the results on the LL double ionization potentials and K-LL Auger energies of H₂S and SO₂ show that the use of a frozen-orbital approximation is preferable to SCF methods for calculation of chemical shifts in K-LL Auger energies and LL ionization potentials. Secondly chemical shifts of K-LL Auger energies of a series of model molecules H₂S, H₂SO₄, H₄SO₂ and H₂SO₂ are correlated with the formal oxidation state of sulphur. This correlation gives a shift of 12 eV in Auger energy per formal charge on sulphur.     

Reconstructing 3-D maps of the local viscoelastic properties using a finite-amplitude modulated radiation force

A modulated acoustic radiation force, produced by two confocal tone-burst ultrasound beams of slightly different frequencies (i.e. 2.0 MHz ± Δf/2, where Δf is the difference frequency), can be used to remotely generate modulated low-frequency (Δf ? 500 Hz) shear waves in attenuating media. By appropriately selecting the duration of the two beams, the energy of the generated shear waves can be concentrated around the difference frequency (i.e., Δf ± Δf/2). In this manner, neither their amplitude nor their phase information is distorted by frequency-dependent effects, thereby, enabling a more accurate reconstruction of the viscoelastic properties. Assuming a Voigt viscoelastic model, this paper describes the use of a finite-element-method model to simulate three-dimensional (3-D) shear-wave propagation in viscoelastic media containing a spherical inclusion. Nonlinear propagation is assumed for the two ultrasound beams, so that higher harmonics are developed in the force and shear spectrum. Finally, an inverse reconstruction algorithm is used to extract 3-D maps of the local shear modulus and viscosity from the simulated shear-displacement fields based on the fundamental and second-harmonic component. The quality of the reconstructed maps is evaluated using the contrast between the inclusion and the background and the contrast-to-noise ratio (CNR). It is shown that the shear modulus can be accurately reconstructed based on the fundamental component, such that the observed contrast deviates from the true contrast by a root-mean-square-error (RMSE) of only 0.38 and the CNR is greater than 30 dB. If the second-harmonic component is used, the RMSE becomes 1.54 and the corresponding CNR decreases by approximately 10–15 dB. The reconstructed shear viscosity maps based on the second harmonic are shown to be of higher quality than those based on the fundamental. The effects of noise are also investigated and a fusion operation between the two spectral components is applied to enhance the reconstruction quality. Finally, a modified shear-wave spectroscopy technique, shown to be more robust to noise, is described for the estimation of the viscoelastic properties inside and outside the spherical inclusion under conditions of increased noise.     

Mapping the local shear modulus and viscosity using a transient finite-amplitude modulated radiation force

Localized narrowband low-frequency shear waves can be non-invasively generated within tissue, by a modulated finite-amplitude radiation force, resulting from the interference of two focused quasi-CW ultrasound beams of slightly different frequencies. Assuming a Voigt viscoelastic model, this paper describes the use of a finite-element-method model, to simulate two-dimensional shear-wave propagation in viscoelastic media, containing circular inclusions (lesions). Using this model, an inverse approach is used to extract maps of the local shear modulus and viscosity. The performance is evaluated based on three metrics: the lesion contrast, the contrast-transfer-efficiency (CTE), and the contrast-to-noise ratio (CNR). Modified definitions of these metrics are proposed and used in order to account for the time-varying nature of the shear waves and the inverse reconstruction algorithm. In the absence of any noise, it is shown that accurate reconstruction can be achieved not only with the fundamental, but also with the higher harmonics, as well as, with a low-frequency component that occurs for high viscosity and high modulation frequencies. For low-viscosity conditions, the lesion contrast, CTE, and CNR are shown to exhibit very good performance not only for the fundamental, but also, for the higher harmonics. In the case of increased viscosities and modulation frequencies, the generated low-frequency component is shown to provide superior contrast performance even when compared to that of the fundamental. The effects of noise on the reconstruction quality are examined. Depending on the lesion and background properties, it is shown that noise can seriously degrade reconstruction from the higher harmonics.     

Theoretical investigation of the complexation of crown ethers and crown ethers of fulleropyrrolidine with (CH3)(x)NH+(4-x), x = 0-4

The electronic and geometric structures of dibenzo-12-crown-4, dibenzo-18-crown-6, and dibenzo-24-crown-8 ethers, and dibenzo-18-crown-6 ether of fullero-N-methylpyrrolidine and their complexes with (CH(3))(x)NH+(4-x), x = 0-4 were investigated by employing density functional theory (B3LYP, M05-2X, M06-2X, MPWBIK and B2PLYP-D) in conjunction with three basis sets. Different energetic minima have been identified for all of the above molecules and complexes in the gas phase as well as in CHCl(3) solvent. We report geometries, complexation energies and some thermochemical data. For increasing values of x, the complexation energies, corrected for the basis set superposition error range from 3.29 to 0.73 eV in the gas phase and from 1.56 to 0.13 eV in the CHCl(3) solvent. In the case of the largest crown ethers, the 24-crown-8 ethers are folded around the ammonium cation so as to maximize the number of hydrogen bonds formed and present the largest complexation energies. Finally, the presence of fullero-N-methylpyrrolidine, attached to the crown ethers, does not change the complexation energies substantially.     

Excited-state intramolecular proton transfer in hydroxyoxime-based chemical sensors

The electronic structure of a series of β-hydroxy-oximes, with different aromatic cores (naphthalene, pyrene, coumarin, pyridine) between the oxime and the hydroxyl groups, has been investigated by time-dependent density functional theory (TDDFT) and of the naphthalene-based oxime, in addition, by resolution-of-identity second-order perturbative coupled cluster (RICC2) calculations with basis sets up to augmented triple-ζ quality. The particular systems have been proposed as fluorescent sensors of organophosphorus (OP) nerve agents, with enhancement of fluorescence accompanying the sensing of OP agents. It is found that the experimentally observed fluorescence quenching of the oxime sensors in their initial form can be attributed to intramolecular proton transfer upon excitation from the β-hydroxyl group to the nitrogen atom, thus forming a weakly emitting hydroxylaminoquinoid.     

Stabilization of the trial method for the Bernoulli problem in case of prescribed Dirichlet data

We apply the trial method for the solution of Bernoulli's free boundary problem when the Dirichlet boundary condition is imposed for the solution of the underlying Laplace equation, and the free boundary is updated according to the Neumann boundary condition. The Dirichlet boundary value problem for the Laplacian is solved by an exponentially convergent boundary element method. The update rule for the free boundary is derived from the linearization of the Neumann data around the actual free boundary. With the help of shape sensitivity analysis and Banach's fixed‐point theorem, we shed light on the convergence of the respective trial method. Especially, we derive a stabilized version of this trial method. Numerical examples validate the theoretical findings.Copyright © 2014 John Wiley & Sons, Ltd.     

Social Isomers of Picolines in a Small Space

Encapsulation complexes permit the observation of molecules under conditions of limited motion. Inside capsules, molecular encounters are prolonged, prearranged, and protected from the medium, in contrast to the short‐lived and random encounters that occur in bulk solution. Herein, the interaction of α‐, β‐, and γ‐picolines in a cylindrical capsule is described. Two picolines were taken up, and NMR spectra indicated dynamic combinations of various social isomers. The stabilities of the complexes are interpreted through computational methods. The shape of the space in the capsule allowed the alignment of molecules and revealed delicate, atom‐to‐atom interactions and attractive forces that elude observation in dilute solution. These weak forces were amplified in the isolated small space of the capsule.     

ChemInform Abstract: Theoretical Study of Gallium Nitride Molecules,GaN2 and GaN4

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