Beam-propagation method based on the Wigner transform: a new formulation

A new formulation of the classical scalar beam-propagation method is derived by use of the Wigner transform. The new method is faster than the classical beam-propagation method because no Fourier transform must be computed. An example given to illustrate the proposed method shows additional advantages.     

Equivariant K-Theory of Compact Connected Lie Groups Dedicated to Daniel Quillen on the Occasion of his Sixtieth Birthday

We compute the equivariant K-theory K _G ^* (G)for a compact connected Lie group Gsuch that ₁ (G)is torsion free (where Gacts on itself by conjugation). We prove that K _G ^* (G)is isomorphic to the algebra of Grothendieck differentials on the representation ring. We also study a special example of a compact connected Lie group Gwith ₁ (G)torsion, namely PSU(3), and compute the corresponding equivariant K-theory.     

Cyclometallated platinum(II) complexes incorporating ethynyl-flavone ligands: switching between triplet and singlet emission induced by selective binding of Pb2+ ions

Platinum-ethynylflavone complexes featuring various polyether arms display (3)IL phosphorescence associated with the appended flavone perturbed by the platinum centre (tau approximately 20 mus), but switch dramatically to flavone-localised (1)IL fluorescence (tau approximately 2 ns) upon selective binding of Pb(2+).     

Periodic homogenization for convex functionals using Mosco convergence

We study the relationship between the Mosco convergence of a sequence of convex proper lower semicontinuous functionals, defined on a reflexive Banach space, and the convergence of their subdifferentiels as maximal monotone graphs. We then apply these results together with the unfolding method (see Cioranescu et al. in C R Math Acad Sci Paris 355:99–104, 2002) to study the homogenization of equations of the form \({-\textrm{ div }d_\varepsilon=f }\), with \({(\nabla u_\varepsilon(x),d_\varepsilon(x)) \in \partial \varphi_\varepsilon(x)}\) where \({\varphi_\varepsilon (x,.)}\) is a Carathéodory convex function with suitable growth and coercivity conditions.     

A universal model for nanoporous carbon supercapacitors applicable to diverse pore regimes, carbon materials, and electrolytes

Supercapacitors, commonly called electric double-layer capacitors (EDLCs), are emerging as a novel type of energy-storage device with the potential to substitute batteries in applications that require high power densities. In response to the latest experimental breakthrough in nanoporous carbon supercapacitors, we propose a heuristic theoretical model that takes pore curvature into account as a replacement for the EDLC model, which is based on a traditional parallel-plate capacitor. When the pore size is in the mesopore regime (2-50 nm), counterions enter mesoporous carbon materials and approach the pore wall to form an electric double-cylinder capacitor (EDCC); in the micropore regime (<2 nm), solvated/desolvated counterions line up along the pore axis to form an electric wire-in-cylinder capacitor (EWCC). In the macropore regime (>50 nm) at which pores are large enough so that pore curvature is no longer significant, the EDCC model can be reduced naturally to the EDLC model. We present density functional theory calculations and detailed analyses of available experimental data in various pore regimes, which show the significant effects of pore curvature on the supercapacitor properties of nanoporous carbon materials. It is shown that the EDCC/EWCC model is universal for carbon supercapacitors with diverse carbon materials, including activated carbon materials, template carbon materials, and novel carbide-derived carbon materials, and with diverse electrolytes, including organic electrolytes, such as tetraethylammonium tetrafluoroborate (TEABF(4)) and tetraethylammonium methylsulfonate (TEAMS) in acetonitrile, aqueous H(2)SO(4) and KOH electrolytes, and even an ionic liquid electrolyte, such as 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMI-TFSI). The EDCC/EWCC model allows the supercapacitor properties to be correlated with pore size, specific surface area, Debye length, electrolyte concentration and dielectric constant, and solute ion size It may lend support for the systematic optimization of the properties of carbon supercapacitors through experiments. On the basis of the insight obtained from the new model, we also discuss the effects of the kinetic solvation/desolvation process, multimodal (versus unimodal) pore size distribution, and exohedral (versus endohedral) capacitors on the electrochemical properties of supercapacitors.     

Theoretical characterization of titanyl phthalocyanine as a p-type organic semiconductor: short intermolecular pi-pi interactions yield large electronic couplings and hole transport bandwidths

The charge-transport properties of the triclinic phase II crystal of titanyl phthalocyanine (alpha-TiOPc) are explored within both a hopping and bandlike regime. Electronic coupling elements in convex- and concave-type dimers are calculated using density functional theory, and the relationship between molecular structure and crystal packing structure in model dimer configurations is considered. Hole transport bandwidths derived from crystal structure dimers are compared to those obtained from electronic band structure calculations; very good agreement between the two approaches is found. The calculations predict large hole bandwidths, on the order of 0.4 eV, and correspondingly very low hole reorganization energies.     

Genotoxicity of combined exposure to polycyclic aromatic hydrocarbons and UVA--a mechanistic study

Abstract Solar UV radiation and benzo[a]pyrene (BaP) are two carcinogenic agents. When combined, their deleterious properties are synergistic. In order to get insights into the underlying processes, we carried out a mechanistic study within isolated DNA photosensitized to UVA radiation by either BaP, its diol epoxide metabolite (BPDE) or the tetraol arising from the hydrolysis of this last molecule. Measurement of the level of the oxidized base 8-oxo-7,8-dihydroguanine revealed that BaP is a poor sensitizer while BPDE and tetraol are more potent ones. None of these compounds was found to photosensitize formation of cyclobutane pyrimidine dimers through triplet energy transfer. On the basis of the distribution of oxidized DNA bases, we could show that photosensitization of DNA by BPDE involves electron abstraction (Type I) while tetraol acts mainly through singlet oxygen production (Type II). Under our experimental conditions, Type I was the major photosensitization process, which shows the lack of involvement of tetraol in the observed photo-oxidation reaction. Finally, we could show that the adducts, resulting from the alkylation of DNA by BPDE, are very potent sensitizers. Indeed, they are located in the close vicinity of the double helix and thus perfectly placed to induce oxidation reactions.     

Unraveling the Photophysical Characteristics,Aromaticity, and Stability of π–Extended Acene-Quinodimethyl Thioamides†

Poly-aromatic systems that contain quinodimethyl (QDM) units are appealing for several photonic and spintronic applications owing to the unique electronic structure, aromaticity, and spin state(s) of the QDM ring. Herein, we report the synthesis and characterization of novel QDM-based chromophores 1 – 3 , which exhibit unique photo-excited behavior and aromaticity. Extending the aromatic core with a biphenyl/phenanthryl- and a pyrrolo-fragment led to reducing the optoelectronic bandgap and modulating the photophysics QDM 1 – 3 . Yet, QDM 2 and 3 suffer from “aromaticity imbalance” and become relatively unstable compared to the parent compound QDM 1 . Further assessment of local aromaticity using computational tools revealed that the pseudo-quinoidal ring B is the main driving force allowing to easily populate the excited triplet state of these chromophores. The present study provides complementary guidelines for designing novel non-classical poly-aromatic systems.