Light scattering by a finite obstacle and fano resonances

The conditions for observing Fano resonances at elastic light scattering by a single finite-size obstacle are discussed. General arguments are illustrated by consideration of the scattering by a small (relative to the incident light wavelength) spherical obstacle based upon the exact Mie solution of the diffraction problem. The most attention is paid to recently discovered anomalous scattering. An exactly solvable one-dimentional discrete model with nonlocal coupling for simulating diffraction in wave scattering in systems with reduced spatial dimensionality is also introduced and analyzed. Deep connections between the resonances in the continuous and discrete systems are revealed.     

Bromoplumbate mit kettenförmigen und isolierten Anionen: (Bzl4P)2[Pb3Br8], (Bzl4P)2[Pb3Br8(dmf)2], (Bzl4P)[PbBr3], (Bzl4P)2[PbBr4] und (Bzl4P)4[Pb2Br6][PbBr4]

Bromoplumbates with One‐dimensional Polymeric and Isolated Anions: (Bzl₄P)₂[Pb₃Br₈], (Bzl₄P)₂[Pb₃Br₈(dmf)₂], (Bzl₄P)[PbBr₃], (Bzl₄P)₂[PbBr₄], and (Bzl₄P)₄[Pb₂Br₆][PbBr₄] PbBr₂ reacts with LiBr and (Bzl₄P)(PF₆) (Bzl = CH₂C₆H₅) in acetone to form a series of bromoplumbate complexes with compositions and structures depending on the conditions of reaction and crystallization. While the anions in (Bzl₄P)₂[Pb₃Br₈] ( 1 ) and (Bzl₄P)[PbBr₃] ( 2 ) are one‐dimensional polymers with penta‐ and hexacoordinated Pb atoms, the metal atoms in the mono‐ and dinuclear complex anions of (Bzl₄P)₂[PbBr₄] · 2acetone ( 3 · 2acetone) and (Bzl₄P)₄[Pb₂Br₆][PbBr₄] ( 4 ) bind to four bromo ligands. From DMF as a solvent (Bzl₄P)₂[Pb₃Br₈(dmf)₂] ( 1 b ) crystallizes with the same bromoplumbate structure as in 1 a , but with dmf ligands occupying the coordination sites vacant in 1 a . Upon radiation of compound 3 with ultraviolet light greenish yellow photoluminescence (emssion maximum at 547 nm) is observed. Crystallographic details see “Inhaltsübersicht”.     

Symmetry‐Breaking Transitions in SmCu1+δAs2—χPχ(δ = 0 — 0.2, χ = 0 — 2). Effect of P and Additional Cu Atoms on Crystal Structures and Magnetic Properties

Crystal structures of the compounds SmCu_1+δAs_2—χP_χ (δ = 0 — 0.2, χ = 0 — 2) undergoing symmetry‐breaking transitions and SmCuP_2.3 have been investigated by the X‐ray single crystal and powder methods. While the phases SmCuAs₂ through SmCuAs_1.22P_0.78 retain the tetragonal HfCuSi₂ structure (P4/nmm space group), the compounds SmCuAs_1.11P_0.89 through SmCuAs_0.56P_1.44 adopt the GdCuAs_1.15P_0.85—type structure (Pmmn space group), an orthorhombic variant of the HfCuSi₂‐type. Further distortion follows in SmCuAs_0.33P_1.67 through SmCuP_2.3, the powder patterns of which were indexed in the P2/n space group (P2/c in a standard setting). According to Landau theory the transitions from tetragonal SmCuAs_1.22P_0.78 to orthorhombic SmCuAs_1.11P_0.89 and from orthorhombic SmCuAs_0.56P_1.44 to monoclinic SmCuAs_0.33P_1.67 can be continuous. Introducing extra copper into some of the orthorhombic arsenophosphides restabilizes tetragonal phases (0 < δ ≤ 0.2) with the P4/nmm symmetry, and the reverse transition Pmmn → P4/nmmcan be continuous. Inserting copper atoms into monoclinic SmCuP₂ yields the SmCu_1+δP₂ phosphides with Cmmm symmetry, and this transition is first‐order. Single crystals of SmCu_1.05As_1.67P_0.33, SmCu_1.07As_0.85P_1.15 and SmCu_1.15P₂ have been prepared using iodine as a mineralizing agent. Their structures have partially occupied Cu sites around the square As/P or P layers and they are a stuffed variant of the HfCuSi₂ structure for SmCu_1.05As_1.67P_0.33 (P4/nmm, a = 3.9163(6), c = 9.932(2)Å), a stuffed GdCuAs_1.15P_0.85 structure for SmCu_1.07As_0.85P_1.15 (Pmmn, a = 3.859(1), b = 3.862(1), c = 9.852(3)Å) and a CeCu_1.12P_1.97‐type structure for SmCu_1.15P₂ (Cmmm, a = 5.453(3), b = 19.511(10), c = 5.439(3)Å). The P net in SmCu_1.15P₂ is broken into rectangular units. The results of magnetic measurements for SmCuAsP are reported.     

Neue Zirconiumphosphatfluoride mit 3D‐Gerüststruktur

New Zirconium Phosphate Fluorides with 3D‐Framework From aqueous solutions of ZrOCl₂, H₃PO₄, HF, and various amines, two new compounds of the general formula [amH₂]_1/2[Zr₂(HPO₄)(PO₄)₂F] · nH₂O ( I : am = N,N‐dimethylethylenediamine, n = 0,5; II : am = N,N‐dimethyl‐1,3‐diaminopropane, n = 0) adopting the ZrPOF‐1 structure type have been synthesized under hydrothermal conditions. In contrast to the monoclinic ZrPOF‐1, both compounds crystallize in the space group P 1 with a = 6.611(3), b = 9.109(4), c = 11.560(5) Å, α = 85.62(4), β = 89.60(4), γ = 70.57(4)° in I , and a = 6.616(2), b = 9.045(3), c = 11.565(4) Å, α = 85.26(4), β = 88.86(4), γ = 71.46(4)° in II . Compound III (am = ethylenediamine, n = 0) has been obtained by dehydration of ZrPOF‐1 and occurs in the space group P1 with a = 6.605(2), b = 8.787(3), c = 11.499(5) Å, α = 93.07(4), β = 90.42(4) and γ = 104.66(4)°. The structural motifs of the frameworks of the three compounds have much in common. The template and the PO₃OH tetrahedra in I and II are disordered. Differences in the water content in both compounds are due to differences in the chain lengths of the amines. The absence of crystal water in compound III breaks the template disordering which is present in ZrPOF‐1. The rotation of the PO₃OH tetrahedra in II and III compared with I and ZrPOF‐1 is discussed in regard with the absence of stabilizing H‐bridges in the former compounds.     

Light Engineering and Silicon Diffractive Optics Assisted Nonparaxial Terahertz Imaging

The art of light engineering unveils a world of possibilities through the meticulous manipulation of photonic properties such as intensity, phase, and polarization. Precision control over these properties finds application in a variety of fields spanning communications, light–matter interactions, laser direct writing, and imaging. Terahertz (THz) range, nestled between microwaves and infrared light, stands out for its remarkable ability to propagate with minimal losses in numerous dielectric materials and compounds, making THz imaging a powerful tool for noninvasive control and inspection. In this study, a rational framework for the design and optimal assembly of nonparaxial THz imaging systems is established. The research is centered on lensless photonic systems composed solely of high-resistivity silicon-based nonparaxial elements such as the Fresnel zone plate, the Fibonacci lens, the Bessel axicon, and the Airy zone plate, all fabricated using laser ablation technology. Through a comprehensive examination through illumination engineering and scattered light collection from raster-scanned samples in a single-pixel detector scheme, the imaging systems are evaluated via diverse metrics including contrast, resolution, depth of field, and focus. These findings chart an exciting course toward the development of compact and user-friendly THz imaging systems where sensors and optical elements seamlessly integrate into a single chip.     

Conformational transitions in macromolecules of complex chemical structure during liquid crystalline ordering

Conformational transitions in thermotropic main-chain polymers of complex chemical structure including homopolymers with possibility of conformational transformations in mesogens and random copolymers (CPLs) containing mesogens of the same type and spacers of different lengths were investigated. It was demonstrated that liquid crystalline (LC) state influences conformational transformations in fragments of chain restraining them in comparison with an isotropic melt. It was found that CPLs studied form LC order of smectic type. Peculiarities in spacers behaviour during transition to LC state ensure formation of such type of LC order. Conclusion about dependence of mechanism of smectic LC order formation on chemical structure of rigid components of CPLs is made.     

Ring‐opening polymerization of cyclic ethers initiated by benzazaphosphole‐W(CO)5/silver hexafluoroantimonate

Attempts to prepare mixed M(0)/Ag⁺ complexes with µ‐bridging P ligands by reaction of benzazaphosphole M(CO)₅ complexes 1a–e (M?W, Mo, Cr) with AgSbF₆ in THF lead to rapid ring‐opening polymerization of this ether at room temperature and, as shown for 1a /AgSbF₆, even at low temperature. Oxetane and epoxides (styrene oxide and cyclohexene oxide) polymerize even more vigorously in the presence of this initiator and require dilution with toluene to control the strongly exothermic reaction. Related P(III)W(CO)₅/AgSbF₆ systems with Ph₃P, (EtO)₃P or 2,4,6‐triphenyl‐phosphinine ligands also initiate the THF polymerization, but less efficiently. Efforts to isolate the initiator complex in other solvents failed because of its high sensitivity to nucleophiles and provided 2a ,characterized by crystal structure analysis as the addition product of methanol at 1a , although 1a itself is stable towards MeOH. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 664–670     

Fractionation of Cellulose

Cellulose samples with molecular weight distributions that are considerably narrower than those of the natural products can be obtained by at least three fundamentally different routes. (i) Synthesis of easily soluble derivatives, fractionation by means of well-established methods and subsequent regeneration, (ii) selective extraction of short chains from activated cellulose, using solvents of suitable marginal quality, and (iii) partition of the homologs between two coexisting phases formed by the demixing of homogeneous solutions. All three methods can be applied successfully. However, the efforts in terms of labor and required solvent differ considerably. Most of the experiments were performed with the following three cellulose samples: Avicel (M _w = 30 kg mol^–1, U = (M _w/M _n)–1 = 2.0), Solucell (M _w = 230 kg mol^–1, U = 1.8), and Stockstadt (M _w = 320 kg mol^–1, U = 5.7). Options (ii) and (iii) emerged most promising for large scale fractionation. The mixed solvent consisting of DMAc and LiCl turned out to be particularly versatile in both cases. In the pure state it can be used for incremental extraction (yielding quick access to orienting information on the width of the molecular weight distribution) as well as for one-step extraction. In combination with suitable precipitants (like acetone) it enables the realization of the coexistence of two liquid phases required with route (iii). One obstacle for fractionation that all methods share is the high viscosity of cellulose solutions. With the last method it is possible to mitigate this limitation considerably by the use of spinning nozzles for the mixing of feed and extracting agent.