Structure Study of Bi2.5Na0.5Ta2O9 and Bi2.5Nam−1.5NbmO3m+3 (m=2-4) by Neutron Powder Diffraction and Electron Microscopy

The crystal structures of Bi_2.5Na_0.5Ta₂O₉ and Bi_2.5Na_m-1.5Nb_mO_3m+3 (m=3,4) have been investigated by the Rietveld analysis of their neutron powder diffraction patterns (λ=1.470 Å). These compounds belong to the Aurivillius phase family and are built up by (Bi₂O₂)²⁺ fluorite layers and (A_m-1B_mO_3m+1)^2- (m=2-4) pseudo-perovskite slabs. Bi_2.5Na_0.5Ta₂O₉ (m=2) and Bi_2.5Na_2.5Nb₄O₁₅ (m=4) crystallize in the orthorhombic space group A2₁am, Z=4, with lattice constants of a=5.4763(4), b=5.4478(4), c=24.9710 (15) and a=5.5095(5), b=5.4783(5), c=40.553(3) Å, respectively. Bi_2.5Na_1.5Nb₃O₁₂ (m=3) has been refined in the orthorhombic space group B2cb, Z=4, with the unit-cell parameters a=5.5024(7), b=5.4622(7), and c=32.735(4) Å. In comparison with its isostructural Nb analogue, the structure of Bi_2.5Na_0.5Ta₂O₉ is less distorted and bond valence sum calculations indicate that the Ta-O bonds are somewhat stronger than the Nb-O bonds. The cell parameters a and b increase with increasing m for the compounds Bi_2.5Na_m-1.5Nb_mO_3m+3 (m=2-4), causing a greater strain in the structure. Electron microscopy studies verify that the intergrowth of mixed perovskite layers, caused by stacking faults, also increases with increasing m.     

TMTHSI,a superior 7-membered ring alkyne containing reagent for strain-promoted azide–alkyne cycloaddition reactions

We describe the development of TMTH-SulfoxImine (TMTHSI) as a superior click reagent. This reagent combines a great reactivity, with small size and low hydrophobicity and compares outstandingly with existing click reagents. TMTHSI can be conveniently functionalized with a variety of linkers allowing attachment of a diversity of small molecules and (peptide, nucleic acid) biologics.

TMTHSI was developed as new reagent for strain-promoted azide–alkyne cycloaddition reactions, enabling connection of a diversity of small to large molecular constructs.     

Linear viscoelastic models: Part I. Relaxation modulus and melt calibration

Constitutive models for the linear viscoelasticity of polymers are presented for the relation between the relaxation modulus and the molecular weight distribution (MWD). We also compute the MWD from a simulated relaxation modulus curve by first obtaining the rheologically effective distribution (RED) as a function of time, and converting this into the MWD by melt calibration; that is, the relation between timescale and the molecular weight. This procedure has similarities with the widely used universal calibration with solved polymers. The main principles of our technique are applied here to familiar relaxation modulus data, for which we present two models: (1) an analytical model derived from control theory, which is known capable of modelling partially observed system and (2) a practical characteristic model for obtaining usable results. No relaxation time or spectrum procedures are used to model the process of linear viscoelastic relaxation. The use of relative calculations and melt calibration dispenses with the need to know the real chain structures such as branching and entangled chain dynamics, and the model remains useful for future investigations of polymer chain structures and dynamics, such as using tube theory.     

Mechanism and dynamics of the CO-induced lifting of the Pt(100) surface reconstruction

The first atomistic simulations of the CO-induced lifting of the Pt(100)-hex reconstruction have been performed. During this phase transformation the surface changes back to bulk-terminated Pt(100)-(1 x 1), whereby the surface atom density decreases by approximately 20%. The simulations reveal a mechanism collective in nature, indicating that restructuring proceeds through ejection of chains of Pt atoms. These chains explain the anisotropy as seen in scanning tunneling microscopy experiments. The restructuring rate depends nonlinearly on the CO coverage, but the absence of local clustering of CO excludes an explanation in terms of elementary reaction kinetics as proposed previously.     

One-dimensional PtO2 at Pt steps: formation and reaction with CO

Using core-level spectroscopy and density functional theory we show that a one-dimensional (1D) oxide structure forms at the steps of the Pt(332) surface after exposure. The 1D oxide is found to be stable in an oxygen pressure range, where bulk oxides are only metastable, and is therefore argued to be a precursor to the Pt oxidation. As an example of the consequences of such a precursor exclusively present at the steps, we investigate the reaction of CO with oxygen covered Pt(332). Albeit more strongly bound, the oxidic oxygen is found to react more easily with CO than oxygen chemisorbed on the Pt terraces.     

Excitation of ground and gamma bands in the 24Mg(α, α')24Mg reaction at 120 MeV

The cross sections for excitation of the members of the ground state (g.s.) band 0^?(g.s.), 2⁺ (1.37 MeV) and 4⁺ (4.12 MeV) and the γ-band 2⁺_γ (4.24 MeV), 3_γ⁺(5.24 MeV) and 4_γ⁺(6.01 MeV) in ²⁴Mg have been measured in inelastic α-scattering at E_α = 120 MeV. The excitation of these states are found to be well described by a coupled-channel calculation (CCBA) performed in the framework of the asymmetric rotational model. Two sets of parameters are found to give excellent fits to the data, but in both a direct coupling between the ground state and the 4⁺ state is found necessary.     

Beta decay studies in the vicinity of 13250Sn82: Excited states in 13051Sb, 13052Te and 13252Te

Using the OSIRIS on-line isotope separator facility, the decays of ¹³⁰Sn and ^{130, 132}Sb have been studied. On the basis of singles γ and γ-γ coincidence Ge(Li) spectra and conversion electron Si(Li) measurements, level schemes for ¹³⁰Sb, ¹³⁰Te and ¹³²Te have been constructed. The corresponding half-lives have been measured using multiscaling technique. The 3.8 min ground state of ¹³⁰Sn populates only positive parity states in the πν^?3 nucleus ¹³⁰Sb: the energetically lowest 5⁺ state with the $\text{(π1}\text{g}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}\text{, ν2}\text{d}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{)}$ configuration assignment; the $\text{T}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 3.6 ± 0.3}\text{ns}\text{4}{}^{\mathrm{+}}$ state at 70.0 keV; the 2⁺ state at 262.5 keV; the (0, 1)⁺ state at 697.2 keV; the 3⁺ state at 813.1 keV and the 1⁺ state at 1042.3 keV excitation energy. A 1.7 min isomeric state in ¹³⁰Sn, with the tentative spin assignment (7^?), populates several odd parity levels in ¹³⁰Sb. These arise from the $\text{(π1}\text{g}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}\text{, ν1}\text{h}{}_{\mathrm{<mtext>11</mtext><mtext>2</mtext>}}{}^{-1}\text{)}$ and/or $\text{(π2}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{, ν1}\text{h}{}_{\mathrm{<mtext>11</mtext><mtext>2</mtext>}}{}^{-1}\text{)}$ configurations and are located 84.7 keV (6^?), 144.9 keV (7^?), 688.5 keV and 1044.0 keV above the 40 min 8^? β- decaying state. No transitions between odd and even parity states have been observed.The most important excited states in ¹³⁰Te found in the β^? decay of the 6.6 min ¹³⁰Sb 5⁺ state are: 839.4 keV, 2⁺; 1632.8 keV, 4⁺; 1815.1 keV, 6⁺; 2100.8 keV, 5^?.Levels in the π²ν^?2 nucleus ¹³²Te were observed in the β^? decays of the 2.8 min ¹³²Sb (4⁺) and the 4.2 min ¹³²Sb (8^?) states. Unique spin and parity assignments have been given to the following states: 973.9 keV, 2⁺; 1670.7 keV, 4⁺; 1774.1 keV, 6⁺; 1924.7 keV, 7^?; 2053.0 keV, 5^?.     

Evidence for double dissociation in K-p interactions at 14.3 GeV/c

We have studied the reaction K^-p → K^-π⁺π^-π⁺π^-p at 14.3 GeV/c to search for evidence of the double dissociation process $\text{K}{}^{\mathrm{-}}\text{p}\text{→}\text{QN}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}{}^1$. In the channel $\text{K}{}^{\mathrm{-}}\text{p}\text{→}\text{K}{}^{10}\text{(890)}$π₁^-π₂^-Δ⁺⁺ (1236) there is evidence for simultaneous production of low-mass enhancements in the $\text{K}{}^{10}\text{π}{}_1{}^{\mathrm{-}}$ and Δ⁺⁺(1236)π₂^- subsystems which correspond to the $\text{Q}\text{→}\text{K}{}^1\text{(890)π}$ and $\text{N}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}{}^1\text{→ Δπ}$ decay modes. In this particular final state the double fragmentation system is produced with a cross section of the order of a few microbarns. Our data are consistent with the factorizable pomeron exchange model of double diffractive dissociation.     

Theoretical studies of aluminoxane chains, rings, cages, and nanostructures

Alumina nanostructures and three families of aluminoxanes, linear, cyclic, and cagelike structures, have structures that resemble their isovalent electronic hydrocarbon analogues. Specific examples of each family are the counterparts of fullerene, allene, benzene, and cubane, respectively. The aluminoxanes and alumina nanostructures are related to each other; the latter can be regarded as a hydrogen- or alkyl-free form of aluminoxane. By exploiting this relationship, the relative stabilities of the three families of aluminoxanes, alumina nanostructures, and alumina crystal lattices have been estimated. According to ab initio calculations, aluminoxane cages, which take the form of a truncated octahedron and related polyhedra, are favored. The stability of the preferred cage, T-symmetric Al28O28H28, is practically equal to that of the alpha-alumina crystal lattice.