Hartree-Fock-Roothaan wave functions,electron density distribution,diamagnetic susceptibility,dipole polarizability and antishielding factor for ions in crystals

Using the Hartree-Fock method the wave functions of Li⁺, Be²⁺, O^2–, F^–, Na⁺, Mg²⁺, Al³⁺, S^2–, Cl^–, K⁺, Ca²⁺, Sc³⁺ and Ti⁴⁺ have been calculated for the free ion and the ion in a potential well. The main result of these calculations is a contraction of the anion and an expansion of the cation due to the external potential. A comparison of the calculations with an experimental determination of the electron density distribution in NaCl and MgO shows qualitative agreement. The diamagnetic susceptibility , the dipole polarizability _d, and the Sternheimer antishielding factor of the ions given above were also calculated for the free ions and the spherical potential ions (SPI). The charged hollow sphere model improves the theoretical values towards the properties determined by experiment.

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Zusammenfassung Unter Verwendung der Hartree-Fock-Methode wurden analytische Wellenfunktionen für die Ionen Li⁺, Be²⁺, O^2–, F^–, Na⁺, Mg²⁺, Al³⁺, S^2–, Cl^–, K⁺, Ca²⁺, Sc³⁺ und Ti⁴⁺ berechnet. Es wurden sowohl die freien Ionen als auch Ionen im Potentialtopf untersucht. Es zeigt sich eine durch das äußere Potential hervorgerufene Kontraktion der Anionen und eine Expansion der Kationen. Der Vergleich der Rechnungen mit experimentellen Bestimmungen der Elektronendichteverteilung in NaCl und MgO zeigt qualitative Übereinstimmung zwischen Theorie und Experiment. Ferner wurden die diamagnetische Suszeptibilität , die Dipolpolarisierbarkeit _d und der Antishieldingfaktor (Sternheimerfaktor) sowohl für die freien als auch für die durch ein kugelsymmetrisches Potential gestörten Ionen berechnet. Das hier benutzte Festkörpermodell der geladenen Hohlkugel ergibt Werte, die in guter Übereinstimmung mit dem Experiment sind.

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Résumé Les fonctions d'onde de Li⁺, Be²⁺, O^2–, F^–, Na⁺, Mg²⁺, Al³⁺, S^2–, Cl^–, K⁺, Ca²⁺, Sc³⁺ et Ti⁴⁺ ont été calculées par la méthode de Hartree-Fock pour l'ion libre et pour l'ion dans un puit de potentiel. Le résultat essentiel de ces calculs montre une contraction de l'anion et une expansion du cation sous l'effet du potentiel extérieur. Les densités électroniques calculées et celles obtenues expérimentalement dans NaCl et MgO sont en accord qualitatif. La susceptibilité diamagnétique , la polarisabilité dipolaire _d, et le facteur anti-écran de Sterneimer des ions ci-dessus ont été calculés pour les ions libres et pour les ions à «potentiel sphérique» (SPI). Le modèle de la sphère creuse chargée améliore les valeurs théoriques par rapport aux données expérimentales.

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D 17 (E. Paschalis, 1967).     

Unitarity constraints for new physics induced by dim-6 operators

We compute the helicity amplitudes for bosonboson scattering at high energy due to the operatorsO _BΦ,O _WΦ andO _UB , and we derive the corresponding unitarity bounds. Thus, we provide relations between the couplings of these operators and the corresponding New Physics thresholds, where either unitarity is saturated or new degrees of freedom are excited. We compare the results with those previously obtained for the operatorsO _W andO _UW and we discuss their implications for direct and indirect tests at present and future colliders. The present treatment completes the study of the unitarity constraints for all blind bosonic operators.     

Cellulose dissolution: insights on the contributions of solvent-induced decrystallization and chain disentanglement

The dissolution of cellulose is a critical step for the efficient utilization of this renewable resource as a starting material for the synthesis of high value-added functional polymers and chemicals and also for biofuel production. The recalcitrance of semicrystalline cellulose microfibrils presents a major barrier to cellulose dissolution. Despite research efforts, important aspects of cellulose dissolution such as solvent-induced decrystallization and chain disentanglement are not well-understood. Here we address these fundamental issues with the practical goal of gaining insights into the swelling and dissolution of cellulose that cannot be obtained from macroscopic experimental data. To this end, we have used a newly-developed phenomenological model that captures the phenomena governing the dissolution of semicrystalline polymers as well as the thermodynamics and kinetics of dissolution. This model fits well experimental data for swelling and dissolution of cotton fibers in the ionic liquid [bmim]Cl, and allows the quantification of two important aspects, i.e., solvent effectiveness in cellulose (1) decrystallization and (2) chain disentanglement, the balance of which controls the mechanism and kinetics of cellulose dissolution. The activation parameters of cellulose decrystallization, estimated using the obtained decrystallization constant values, reveal that the decrystallization of cellulose in [bmim]Cl is associated with positive enthalpy and entropy and it is also very sensitive to temperature. When the solvent effectiveness in the disruption of cellulose crystals is relatively lower than its ability to disentangle the chains, the kinetics of dissolution are controlled by decrystallization. Furthermore, conditions that facilitate cellulose chain disentanglement, in addition to increasing the rate of dissolution, can result in faster decrystallization. The solvent effectiveness in chain disentanglement is the only factor that determines the decrease of the cellulose fiber radius. In cases where the fiber dissolution rate is lower than the decrystallization rate, the dissolution of cellulose is mostly controlled by the solvent ability to disentangle the chains. The insights obtained from this study improve the understanding of cellulose–solvent interactions underlying decrystallization and disentanglement and their contributions in controlling the kinetics of cellulose swelling and dissolution.     

Facile aqueous synthesis and stabilization of nearly monodispersed gold nanospheres by poly(L‐proline)

A facile strategy is developed to synthesize Au nanoparticles (Au‐NPs) using water‐soluble poly(L ‐proline) (PLP). The synthesized NPs were characterized by TEM, FTIR and NMR spectroscopy, thermogravimetric analysis, and circular dichroism. It was found that PLP has a “dual” role as an efficient reductant of Au(III) and simultaneously as a stabilizing agent of Au‐NPs. The influence of PLP molecular weight, temperature, initial Au(III) concentration, and Au(III)/PLP molar ratio on the size and dispersity of Au‐NPs is examined. It was found that the unique extended secondary structure of PLP II resulted in the facile formation of highly crystalline Au‐NPs in water at a very low Au(III)/PLP molar ratio. These Au‐NPs have the smallest dimensions and size distributions among NPs synthesized so far by polymeric materials in aqueous media, and exhibit enduring colloidal stability. Therefore, by utilizing biocompatible and benign materials in water, we managed to obtain Au‐NPs, so as the final product is ready‐to‐use for biomedical applications. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Structure and dynamics of dextran in binary mixtures of a good and a bad solvent

The structure and dynamics of the common polysaccharide dextran have been investigated in mixed solvents at two different temperatures using small-angle X-ray scattering (SAXS) and viscosity measurements. More specifically, binary mixtures of a good solvent (water, formamide, dimethylsulfoxide, ethanolamine) and the bad solvent ethanol as the minority component have been considered. The experimentally observed effects on the polymer conformation (intrinsic viscosity, coil radius, and radius of gyration) of the bad solvent addition are discussed in terms of hydrogen bonding density and are correlated with the Hansen solubility parameters and the surface tension of the solvent mixtures. Hydrogen bonding appears to be an important contributor to the solubility of dextran but is not sufficient to capture the dextran coil contraction in the mixtures of good+bad solvents.     

O-Directed free-radical hydrostannations of propargyl ethers, acetals, and alcohols with Ph3SnH and Et3B

[reaction: see text] The O-directed hydrostannation of various propargyloxy substrates is reported with Ph(3)SnH/Et(3)B.     

Feasibility studies of the EXL setup for FAIR using the GSI storage ring ESR

The investigation of light-ion induced direct reactions in inverse kinematics, using stored and cooled radioactive beams, interacting with internal H, He, etc. gas-jet targets, bears a large potential for nuclear structure and astrophysics studies on exotic nuclei. An extended research project EXL has been accepted for the future facility FAIR in Darmstadt, Germany. In order to explore the experimental conditions for measurements planned at FAIR, a first test experiment for proving the feasibility of the EXL concept was performed.     

Meson decays in the non-relativistic quark model

Treating light as well as heavy pseudoscalar and vector mesons as non-relativistic quarkonia, we calculate various decay modes, including lowest QCD corrections. All decay modes studied are in good agreement with experiment, indicating that the quarkonium treatment is applicable to light mesons η, η′, π, also. Consistency of the quarkonium and current algebra treatments for the process π⁰ → 2λ leads to $\text{f}{}_{\mathrm{\pi }}\text{= (}\text{3}\text{2π}\text{)m}{}_{\mathrm{<mtext>u</mtext>}}\text{{1 ? (0.62/4π)α}{}_{\mathrm{<mtext>s</mtext>}}\text{(μ)},}\text{where}\text{m}{}_{\mathrm{<mtext>u</mtext>}}$ is the constituent u-quark mass, and $\text{f}{}_{\mathrm{\pi }}\text{? 93}\text{MeV}$.     

Using nonuniform electric fields to accelerate the transport of viruses to surfaces from media of physiological ionic strength

Nonuniform ac (alternating current) electric fields created by microelectrodes are investigated for their influence on the transport of the vesicular stomatitis virus (VSV) from aqueous suspensions of physiological ionic strength to surfaces on which the VSV is captured. Whereas passive diffusion did not lead to detectable levels of virus captured on a surface when using titers of VSV as high as 107 PFU/mL, nonuniform electric field-mediated transport led to the detection of 105 PFU/mL of virus in 2 min. An order-of-magnitude analysis of the time scales associated with virus transport to the microelectrodes inside media of physiological relevance indicates that electrothermal fluid flow (and the resulting viscous drag forces on the virus) rather than dielectrophoresis likely constitutes the major mechanism for virus transport far from the electrodes. The influence of dielectrophoresis was calculated to be confined to a region within a few micrometers of the electrodes and to lead to collection patterns of both virus and fluorescently labeled particles near the electrodes that were found to be in qualitative agreement with experiments. These observations and conclusions are discussed within a theoretical framework presented in the paper. The results presented in this work, when combined, suggest that ac electrokinetic phenomena can be used to expeditiously transport and capture viruses onto surfaces from solutions of high ionic strength, thus providing a potentially useful approach to addressing a bottleneck in the development of devices that allow for rapid sampling and detection of infectious biological agents.