Picosecond pulse radiolysis of aromatic solutes in cyclohexane: formation of solute triplet states

Evolution of the absorption spectra due to transient species produced by the pulse radiolysis of biphenyl, pyrene, diphenylamine, and naphthalene in cyclohexane was measured over 50 ps to 3 ns. The initial (50 ps) yield of triplet is only a small fraction of the yield (G ≈ 0.3) at 3 ns.     

Picosecond molecular relaxations during electron solvation in liquid alcohol and alcohol-alkane solutions

The time evolution of the solvated electron in a series of linear alcohols has been measured. A correlation between the time for monomer rotation τ₂ and the solvation time τ_s seems to hold for the series. The mechanism of solvation is discussed with reference to the experimental data.     

Existence and Strong Uncountability

On the standard view for something to exist is for one thing to exist: in slogan form, to be is to be countable (cf. van Inwagen 2009). E.J. Lowe (2009, 2003, 1998) argues something can exist without being countable as one, however. His primary example is homogenous “stuff,” i.e., qualitatively uniform and infinitely divisible matter. Lacking nonarbitrary boundaries and being everywhere the same, homogenous stuff lacks a principle of individuation that would yield countably distinct constituents. So, for Lowe, homogenous stuff is strongly uncountable. Olson (2011) rejects Lowe’s view and defends the orthodox connection between existence and number. He argues that if there is any stuff, there is a (determinate) number of portions of stuff. Sider (2011, 2001) also rejects a stuff ontology, claiming it is incompatible with his preferred view that the familiar quantifiers of predicate logic carve at nature’s joints. Against these arguments, I defend the uncountability of stuff and the possibility of existence without countability. If to be is to be countable, more is needed than the arguments that Olson and Sider provide.     

The matching problem has no small symmetric SDP

Yannakakis (Proceedings of the STOC, pp 223–228, 1988; J Comput Syst Sci 43(3):441–466, 1991. doi: 10.1016/0022-0000(91)90024-Y) showed that the matching problem does not have a small symmetric linear program. Rothvoß (Proceedings of the STOC, pp 263–272, 2014) recently proved that any, not necessarily symmetric, linear program also has exponential size. In light of this, it is natural to ask whether the matching problem can be expressed compactly in a framework such as semidefinite programming (SDP) that is more powerful than linear programming but still allows efficient optimization. We answer this question negatively for symmetric SDPs: any symmetric SDP for the matching problem has exponential size. We also show that an O(k)-round Lasserre SDP relaxation for the asymmetric metric traveling salesperson problem yields at least as good an approximation as any symmetric SDP relaxation of size \(n^{k}\). The key technical ingredient underlying both these results is an upper bound on the degree needed to derive polynomial identities that hold over the space of matchings or traveling salesperson tours.     

Electronic structure of the water oxidation catalyst cis,cis-[(bpy)2(H2O)Ru(III)ORu(III)(OH2)(bpy)2]4+, the blue dimer

The first designed molecular catalyst for water oxidation is the "blue dimer", cis,cis-[(bpy)(2)(H(2)O)Ru(III)ORu(III)(OH(2))(bpy)(2)](4+). Although there is experimental evidence for extensive electronic coupling across the μ-oxo bridge, results of earlier DFT and CASSCF calculations provide a model with magnetic interactions of weak to moderately coupled Ru(III) ions across the μ-oxo bridge. We present the results of a comprehensive experimental investigation, combined with DFT calculations. The experiments demonstrate both that there is strong electronic coupling in the blue dimer and that its effects are profound. Experimental evidence has been obtained from molecular structures and key bond distances by XRD, electrochemically measured comproportionation constants for mixed-valence equilibria, temperature-dependent magnetism, chemical properties (solvent exchange, redox potentials, and pK(a) values), XPS binding energies, analysis of excitation-dependent resonance Raman profiles, and DFT analysis of electronic absorption spectra. The spectrum can be assigned based on a singlet ground state with specific hydrogen-bonding interactions with solvent molecules included. The results are in good agreement with available experimental data. The DFT analysis provides assignments for characteristic absorption bands in the near-IR and visible regions. Bridge-based dπ → dπ* and interconfiguration transitions at Ru(III) appear in the near-IR and MLCT and LMCT transitions in the visible. Reasonable values are also provided by DFT analysis for experimentally observed bond distances and redox potentials. The observed temperature-dependent magnetism of the blue dimer is consistent with a delocalized, diamagnetic singlet state (dπ(1)*)(2) with a low-lying, paramagnetic triplet state (dπ(1)*)(1)(dπ(2)*)(1). Systematic structural-magnetic-IR correlations are observed between ν(sym)(RuORu) and ν(asym)(RuORu) vibrational energies and magnetic properties in a series of ruthenium-based, μ-oxo-bridged complexes. Consistent with the DFT electronic structure model, bending along the Ru-O-Ru axis arises from a Jahn-Teller distortion with ∠Ru-O-Ru dictated by the distortion and electron-electron repulsion.     

Synthesis and thermal characterization of NZP compounds Na1?xLixZr2(PO4)3 (x?=?0.00–0.75)

Sodium zirconium phosphate (NZP) composition Na_1−x Li _x Zr₂(PO₄)₃, x = 0.00–0.75 has been synthesized by method of solid state reaction method from Na₂CO₃·H₂O, Li₂CO₃, ZrO₂, and NH₄H₂PO₄, sintering at 1050–1250 °C for 8 h only in other to determine the effect on thermal properties, such as the phase formation of the compound. The materials have been characterized by TGA and DTA thermal analysis methods from room temperature to 1000 °C. It was observed that the increase in lithium content of the samples increased thermal stability of the samples and the DTA peaks shifted towards higher temperatures with increase in lithium content. The thermal stability regions for all the sample was observed to be from 640 °C. The sample with the highest lithium content, x = 0.75, exhibited the greatest thermal stability over the temperature range.     

Production of uniformly sized serum albumin and dextrose microbubbles

Uniformly-sized preparations with average microbubble (MB) diameters from 1 to 7 μm were produced reliably by sonicating decafluorobutane-saturated solutions of serum albumin and dextrose. Detailed protocols for producing and size-separating the MBs are presented, along with the effects that changing each production parameter (serum albumin concentration, sonication power, sonication time, etc.) had on MB size distribution and acoustic stability. These protocols can be used to produce MBs for experimental applications or serve as templates for developing new protocols that yield MBs with physical and acoustic properties better suited to specific applications. Size stability and ultrasonic performance quality control tests were developed to assure that successive MB preparations perform identically and to distinguish the physical and acoustic properties of identically sized MBs produced with different serum albumin-dextrose formulations and sonication parameters. MBs can be stored at 5 °C for protracted periods (2 weeks to one year depending on formulation).