Excitation Energy Delocalization and Transfer to Guests within M(II)4L6 Cage Frameworks

We have prepared a series of M(II)4L6 tetrahedral cages containing one or the other of two distinct BODIPY moieties, as well as mixed cages that contain both BODIPY chromophores. The photophysical properties of these cages and their fullerene-encapsulated adducts were studied in depth. Upon cage formation, the charge-transfer character exhibited by the bis(aminophenyl)-BODIPY subcomponents disappeared. Strong excitonic interactions were instead observed between at least two BODIPY chromophores along the edges of the cages, arising from the electronic delocalization through the metal centers. This excited-state delocalization contrasts with previously reported cages. All cages exhibited the same progression from an initial bright singlet state (species I) to a delocalized dark state (species II), driven by interactions between the transition dipoles of the ligands, and subsequently into geometrically relaxed species III. In the case of cages loaded with C60 or C70 fullerenes, ultrafast host-to-guest electron transfer was observed to compete with the excitonic interactions, short-circuiting the I → II → III sequence

Controlling the structures of organic semiconductor–quantum dot nanocomposites through ligand shell chemistry

Nanocrystal quantum dots (QD) functionalised with active organic ligands hold significant promise as solar energy conversion materials, capable of multiexcitonic processes that could improve the efficiencies of single-junction photovoltaic devices. Small-angle X-ray and neutron scattering (SAXS and SANS) were used to characterize the structure of lead sulphide QDs post ligand-exchange with model acene-carboxylic acid ligands (benzoic acid, hydrocinnamic acid and naphthoic acid). Results demonstrate that hydrocinnamic acid and naphthoic acid ligated QDs form monolayer ligand shells, whilst benzoic acid ligated QDs possess ligand shells thicker than a monolayer. Further, the formation of a range of nanocomposite materials through the self-assembly of such acene-ligated QDs with an organic small-molecule semiconductor [5,12-bis((triisopropylsilyl)ethynyl)tetracene (TIPS-Tc)] is investigated. These materials are representative of a wider set of functional solar energy materials; here the focus is on structural studies, and their optoelectronic function is not investigated. As TIPS-Tc concentrations are increased, approaching the solubility limit, SANS data show that QD fractal-like features form, with structures possibly consistent with a diffusion limited aggregation mechanism. These, it is likely, act as heterogeneous nucleation agents for TIPS-Tc crystallization, generating agglomerates containing both QDs and TIPS-Tc. Within the TIPS-Tc crystals there seem to be three distinct QD morphologies: (i) at the crystallite centre (fractal-like QD aggregates acting as nucleating agents), (ii) trapped within the growing crystallite (giving rise to QD features ordered as sticky hard spheres), and (iii) a population of aggregate QDs at the periphery of the crystalline interface that were expelled from the growing TIPS-Tc crystal. Exposure of the QD:TIPS-Tc crystals to DMF vapour, a solvent known to be able to strip ligands from QDs, alters the spacing between PbS–hydrocinnamic acid and PbS–naphthoic acid ligated QD aggregate features. In contrast, for PbS–benzoic acid ligated QDs, DMF vapour exposure promotes the formation of ordered QD colloidal crystal type phases. This work thus demonstrates how different QD ligand chemistries control the interactions between QDs and an organic small molecule, leading to widely differing self-assembly processes. It highlights the unique capabilities of multiscale X-ray and neutron scattering in characterising such composite materials

Community Structure in Congressional Cosponsorship Networks

We study the United States Congress by constructing networks between Members of Congress based on the legislation that they cosponsor. Using the concept of modularity, we identify the community structure of Congressmen, as connected via sponsorship/cosponsorship of the same legislation, to investigate the collaborative communities of legislators in both chambers of Congress. This analysis yields an explicit and conceptually clear measure of political polarization, demonstrating a sharp increase in partisan polarization which preceded and then culminated in the 104th Congress (1995-1996), when Republicans took control of both chambers. Although polarization has since waned in the U.S. Senate, it remains at historically high levels in the House of Representatives.Comment: 8 pages, 4 figures (some with multiple parts), to appear in Physica A; additional background info and explanations added from last versio

Large scale numerical investigation of excited states in poly(phenylene)

A density matrix renormalisation group scheme is developed, allowing for the first time essentially exact numerical solutions for the important excited states of a realistic semi-empirical model for oligo-phenylenes. By monitoring the evolution of the energies with chain length and comparing them to the experimental absorption peaks of oligomers and thin films, we assign the four characteristic absorption peaks of phenyl-based polymers. We also determine the position and nature of the nonlinear optical states in this model.Comment: RevTeX, 10 pages, 4 eps figures included using eps

Mixed small-molecule matrices improve nanoparticle dispersibility in organic semiconductor-nanoparticle films

Controlling the dispersibility of nanocrystalline inorganic quantum dots (QDs) within organic semiconductor (OSC):QD nanocomposite films is critical for a wide range of optoelectronic devices. This work demonstrates how small changes to the OSC host molecule can have a dramatic detrimental effect on QD dispersibility within the host organic semiconductor matrix as quantified by grazing incidence X-ray scattering. It is commonplace to modify QD surface chemistry to enhance QD dispersibility within an OSC host. Here, an alternative route toward optimizing QD dispersibilities is demonstrated, which dramatically improves QD dispersibilities through blending two different OSCs to form a fully mixed OSC matrix phase

Insights into the kinetics and self-assembly order of small-molecule organic semiconductor/quantum dot blends during blade coating

Organic–inorganic nanocomposite films formed from blends of small-molecule organic semiconductors and colloidal quantum dots are attractive candidates for high efficiency, low-cost solar energy harvesting devices. Understanding and controlling the self-assembly of the resulting organic–inorganic nanocomposite films is crucial in optimising device performance, not only at a lab-scale but for large-scale, high-throughput printing and coating methods. Here, in situ grazing incidence X-ray scattering (GIXS) gives direct insights into how small-molecule organic semiconductors and colloidal quantum dots self-assemble during blade coating. Results show that for two blends separated only by a small difference in the structure of the small molecule forming the organic phase, crystallisation may proceed down two distinct routes. It either occurs spontaneously or is mediated by the formation of quantum dot aggregates. Irrespective of the initial crystallisation route, the small-molecule crystallisation acts to exclude the quantum dot inclusions from the growing crystalline matrix phase. These results provide important fundamental understanding of structure formation in nanocomposite films of organic small molecules and colloidal quantum dots prepared via solution processing routes. It highlights the fundamental difference to structural evolution which can be made by seemingly small changes in system composition. It provides routes for the structural design and optimisation of solution-processed nanocomposites that are compatible with the large-scale deposition manufacturing techniques that are crucial in driving their wider adoption in energy harvesting applications

Electroexcitation of the Δ+(1232)\Delta^{+}(1232) at low momentum transfer

We report on new p$(e,e^\prime p)\pi^\circ$ measurements at the $\Delta^{+}(1232)$ resonance at the low momentum transfer region. The mesonic cloud dynamics is predicted to be dominant and rapidly changing in this kinematic region offering a test bed for chiral effective field theory calculations. The new data explore the low $Q^2$ dependence of the resonant quadrupole amplitudes while extending the measurements of the Coulomb quadrupole amplitude to the lowest momentum transfer ever reached. The results disagree with predictions of constituent quark models and are in reasonable agreement with dynamical calculations that include pion cloud effects, chiral effective field theory and lattice calculations. The reported measurements suggest that improvement is required to the theoretical calculations and provide valuable input that will allow their refinements

Measurement of νˉμ\bar{\nu}_{\mu} and νμ\nu_{\mu} charged current inclusive cross sections and their ratio with the T2K off-axis near detector

We report a measurement of cross section $\sigma(\nu_{\mu}+{\rm nucleus}\rightarrow\mu^{-}+X)$ and the first measurements of the cross section $\sigma(\bar{\nu}_{\mu}+{\rm nucleus}\rightarrow\mu^{+}+X)$ and their ratio $R(\frac{\sigma(\bar \nu)}{\sigma(\nu)})$ at (anti-)neutrino energies below 1.5 GeV. We determine the single momentum bin cross section measurements, averaged over the T2K $\bar{\nu}/\nu$-flux, for the detector target material (mainly Carbon, Oxygen, Hydrogen and Copper) with phase space restricted laboratory frame kinematics of $\theta_{\mu}$500 MeV/c. The results are $\sigma(\bar{\nu})=\left( 0.900\pm0.029{\rm (stat.)}\pm0.088{\rm (syst.)}\right)\times10^{-39}$ and $\sigma(\nu)=\left( 2.41\ \pm0.022{\rm{(stat.)}}\pm0.231{\rm (syst.)}\ \right)\times10^{-39}$in units of cm$^{2}$/nucleon and$R\left(\frac{\sigma(\bar{\nu})}{\sigma(\nu)}\right)= 0.373\pm0.012{\rm (stat.)}\pm0.015{\rm (syst.)}$.Comment: 18 pages, 8 figure

Terrestrial modification of the Ivuna meteorite and a reassessment of the chemical composition of the CI type specimen

The rare CI carbonaceous chondrites are the most aqueously altered and chemically primitive meteorites but due to their porous nature and high abundance of volatile elements are susceptible to terrestrial weathering. The Ivuna meteorite, type specimen for the CI chondrites, is the largest twentieth-century CI fall and probably the CI chondrite least affected by terrestrial alteration that is available for study. The main mass of Ivuna (BM2008 M1) has been stored in a nitrogen atmosphere at least since its arrival at the Natural History Museum (NHM), London, in 2008 (70 years after its fall) and could be considered the most pristine CI chondrite stone. We report the mineralogy, petrography and bulk elemental composition of BM2008 M1 and a second Ivuna stone (BM1996 M4) stored in air within wooden cabinets. We find that both Ivuna stones are breccias consisting of multiple rounded, phyllosilicate-rich clasts that formed through aqueous alteration followed by impact processing. A polished thin section of BM2008 M1 analysed immediately after preparation was found to contain sulphate-bearing veins that formed when primary sulphides reacted with oxygen and atmospheric water. A section of BM1996 M4 lacked veins but had sulphate grains on the surface that formed in ≤6 years, ∼3 times faster than previous reports for CI chondrite sections. Differences in the extent of terrestrial alteration recorded by BM2008 M1 and BM1996 M4 probably reflect variations in the post-recovery curation history of the stones prior to entering the NHM collection, and indicate that where possible pristine samples of hydrated carbonaceous should be kept out of the terrestrial environment in a stable atmosphere to avoid modification. The bulk elemental composition of the two Ivuna stones show some variability due to their heterogeneous nature but in general are similar to previous analyses of CI chondrites. We combine our elemental abundances with literature values to calculate a new average composition for the Ivuna meteorite, which we find is in good agreement with existing compilations of element compositions in the CI chondrites and the most recent solar photospheric abundances

Methane and carbon dioxide fluxes and their regional scalability for the European Arctic wetlands during the MAMM project in summer 2012

Airborne and ground-based measurements of methane (CH4), carbon dioxide (CO2) and boundary layer thermodynamics were recorded over the Fennoscandian landscape (67–69.5° N, 20–28° E) in July 2012 as part of the MAMM (Methane and other greenhouse gases in the Arctic: Measurements, process studies and Modelling) field campaign. Employing these airborne measurements and a simple boundary layer box model, net regional-scale (~ 100 km) fluxes were calculated to be 1.2 ± 0.5 mg CH4 h−1 m−2 and −350 ± 143 mg CO2 h−1 m−2. These airborne fluxes were found to be relatively consistent with seasonally averaged surface chamber (1.3 ± 1.0 mg CH4 h−1 m−2) and eddy covariance (1.3 ± 0.3 mg CH4 h−1 m−2 and −309 ± 306 mg CO2 h−1 m−2) flux measurements in the local area. The internal consistency of the aircraft-derived fluxes across a wide swath of Fennoscandia coupled with an excellent statistical comparison with local seasonally averaged ground-based measurements demonstrates the potential scalability of such localised measurements to regional-scale representativeness. Comparisons were also made to longer-term regional CH4 climatologies from the JULES (Joint UK Land Environment Simulator) and HYBRID8 land surface models within the area of the MAMM campaign. The average hourly emission flux output for the summer period (July–August) for the year 2012 was 0.084 mg CH4 h−1 m−2 (minimum 0.0 and maximum 0.21 mg CH4 h−1 m−2) for the JULES model and 0.088 mg CH4 h−1 m−2 (minimum 0.0008 and maximum 1.53 mg CH4 h−1 m−2) for HYBRID8. Based on these observations both models were found to significantly underestimate the CH4 emission flux in this region, which was linked to the under-prediction of the wetland extents generated by the models