Direct evaluation of the lifetime matrix by the hyperquantization algorithm: narrow resonances in the F + H2 reaction dynamics and their splitting for nonzero angular momentum

We propose a new method for the direct and efficient evaluation of the Felix Smith's lifetime Q matrix for reactive scattering problems. Simultaneous propagation of the solution to a set of close-coupled equations together with its energy derivative allows one to avoid common problems pertinent to the finite-difference approach. The procedure is implemented on a reactive scattering code which employs the hyperquantization algorithm and the Johnson-Manolopoulos [J. Comput. Phys. 13, 455 (1973); J. Chem. Phys 85, 6425 (1986)] propagation to obtain the complete S matrix and scattering observables. As an application of the developed formalism, we focus on the total angular momentum dependence of narrow under-barrier resonances supported by van der Waals wells of the title reaction. Using our method, we fully characterize these metastable states obtaining their positions and lifetimes from Lorentzian fits to the largest eigenvalue of the lifetime matrix. Remarkable splittings of the resonances observed at J>0 are rationalized in terms of a hyperspherical model. In order to provide an insight on the decay mechanism, the Q-matrix eigenvectors are analyzed and the dominant channels populated during the decomposition of metastable states are determined. Possible relevance of the present results to reactive scattering experiments is discussed.     

Pore Aperture Control Toward Size-Exclusion-Based Hydrocarbon Separations

Metal–organic frameworks (MOFs) have been proposed as a promising material for non-thermal chemical separations owing to their high structural diversity and tunability. Here, we report the synthesis of a zinc-based MOF containing a three-dimensional (3D) linker, bicyclo[2.2.2]octane-1,4-dicarboxylic acid, with high thermal stability towards the separation of hexane isomers. The incorporation of the 3D linker enhances the structural stability and provides well-defined pore apertures/channels with sub-Ångstrom precision. This precision allowed for the separation of similarly sized hexane isomers based on subtle differences in their kinetic diameters. Multi-component liquid phase batch experiments confirmed the separation of hexanes mixture into linear, monobranched, and dibranched isomers. This work represents a significant milestone in the construction of stable Zn-based MOFs and the incorporation of 3D linkers as a potential solution to challenging separations.     

Photoelectron spectroscopy of the Cl(-)...H(2)D(2) anions: a model beyond the rotationless and Franck-Condon approximations

A model for simulating photoelectron spectra of the triatomic van der Waals complexes containing stable atomic anion and diatomic molecule is proposed and applied to the Cl(-)...H(2) and Cl(-)...D(2) anions. The model assumes adiabatic separation of the electronic and nuclear motions and localization of the photodetachment act at the atomic chromophore. Under these approximations, the electronic transition dipole moment matrix elements are evaluated using the atoms-in-molecule approach and explicit expressions for the rovibrational line strength factors are derived. The energies and intensities of a number of rovibronic photoelectron transitions are calculated for the Cl(-)...H(2) and Cl(-)...D(2) anions within the adiabatic bender model, i.e., with the full separation of the vibrational motions, whereas the simulations of the broad spectral envelopes are performed using the equilibrium conditions, asymmetric line shape function, and two choices of the relative abundances of the para- and ortho-forms of the complex. The simulations reproduce experimental spectra reasonably well allowing for their unambiguous assignment in terms of vibronic transitions fully consistent with the previous time-dependent calculations. Agreement with the previous theoretical works, manifestations of non-Franck-Condon effects, and implications to the assessment of the neutral potential energy surfaces are discussed.     

Cosmic-ray antiproton constraints on light singlino-like dark matter candidates

The CoGeNT experiment, dedicated to direct detection of dark matter, has recently released excess events that could be interpreted as elastic collisions of ∼10 GeV dark matter particles, which might simultaneously explain the still mysterious DAMA/LIBRA modulation signals, while in conflict with results from other experiments such as CDMS, XENON-100 and SIMPLE. It was shown that 5-15 GeV singlino-like dark matter candidates arising in singlet extensions of minimal supersymmetric scenarios can fit these data; annihilation then mostly proceeds into light singlet-dominated Higgs (pseudo-)scalar fields. We develop an effective Lagrangian approach to confront these models with the existing data on cosmic-ray antiprotons, including the latest PAMELA data. Focusing on a parameter space consistent with the CoGeNT region, we show that the predicted antiproton flux is generically in tension with the data whenever the produced (pseudo-)scalars can decay into quarks energetic enough to produce antiprotons, provided the annihilation S-wave is significant at freeze out in the early universe. In this regime, a bound on the singlino annihilation cross section is obtained, 〈σv〉?¹⁰−26 cm³/s, assuming a dynamically constrained halo density profile with a local value of ρ_⊙=0.4 GeV/cm³. Finally, we provide indications on how PAMELA or AMS-02 could further constrain or detect those configurations producing antiprotons which are not yet excluded.     

On the dependence of the properties of glasses on cooling and heating rates II: Prigogine-Defay ratio, fictive temperature and fictive pressure

In a previous analysis (J. Chem. Phys. 125 (2006) 094505) it was shown by us that - in contrast to earlier believe - a satisfactory theoretical interpretation of the experimentally measured values of the so-called Prigogine-Defay ratio, Π, can be given employing only one structural order parameter. According to this analysis, the value of this ratio has to be, in accordance with experimental findings, larger than one (Π > 1). This analysis is extended here and, in particular, the dependence of the value of Π on cooling and heating rates is studied. Finally, employing the general model-independent definition of internal (fictive) pressure and fictive temperature, developed by us (J. Non-Crystalline Solids 355 (2009) 653), it is shown how these parameters behave in dependence on temperature for different sets of cooling and heating rates. Some further consequences and possible extensions are discussed briefly.     

Biocentri-voltammetric biosensor for acetylcholine and choline

We report on the determination of choline and acetylcholine via biocentrivoltammetry. This method combines centrifugation and voltammetry and is based on a carbon paste electrode modified with acetylcholinesterase and choline oxidase. The electrode was placed at the bottom of a biocentrivoltammetric cell. Acetylcholine and choline are accumulated on the enzyme electrode via centrifugative forces, upon which a direct voltammetric scan is applied. Reaction time, pH values, quantities of enzyme and centrifugation parameters were optimized. A linear response is obtained in the 0.07 to 10?μM concentration range of acetylcholine, and a limit of detection as low as 0.5?μM. The linear range is between 0.1 and 500?μM for choline. The method was applied to the determination of acetylcholine and choline in spiked serum samples.

A New Approach for in vitro Imaging of Breast Cancer Cells by Anti‐Metadherin Targeted PVA‐Pyrene

Poly(vinyl alcohol)‐pyrene‐anti‐metadherin (PVA‐Py‐(Anti‐MTDH)), a novel antibody based water soluble probe containing both fluorescent and target sites in the structure for in vitro imaging of breast cancer cells is reported here. Since breast cancer cells have an excess of MDTH protein expressed on the surface, a PVA‐Py prepared by “Click chemistry” approach is targeted by Anti‐MTDH antibody and applied to the MCF‐7 cell line. After characterization, the designed architecture was evaluated in terms of cell incorporation efficiency and compared with a non‐targeted structure (PVA‐Py). Atomic force microscopy (AFM) and fluorescence microscopy images of cells after incubation of the probe molecules were also obtained to monitor the interaction of the probes with the cancerous cells.

     

Synthesis and luminescence properties of Ho3+ doped Y2O3 submicron particles

This paper presents comprehensive results of the eco-friendly, large scale fabrication of nearly spherical Ho³⁺-doped Y₂O₃ submicron particles, synthesized using the urea homogeneous precipitation method. The dependence of the photoluminescence emission on the doping concentration was examined to determine the optimum Ho³⁺ concentration in the samples. X-ray diffraction data of the Y₂O₃:Ho³⁺ particles revealed a cubic Y₂O₃ structure. Field emission scanning electron microscopy confirmed the formation of nearly spherical shape particles with a mean diameter of 200±50 nm. The luminescence emission intensity significantly increased with increasing calcination temperature due to the improved crystallinity of the synthesized particles. Strong visible green-yellowish emission due to ⁵F₄; ⁵S₂–⁵I₈ Stokes transitions was observed under constant 450 nm excitation. Simple large scale fabrication along with the strong visible green-yellowish emission might give these particles wide area of applications.