Electronic structure of the self-trapped exciton in the potassium halides

We present pseudopotential calculations of the energy levels and wave-functions of the electron associated with the self-trapped exciton in KCl, KBr and KI. Accurate values are obtained for the separation of the singlet and triplet luminescent bands, for the electronic transitions, and for the spin resonance linewidths. Lattice distortion is shown to be particularly important in KCl. Additional low-energy electronic transitions, at 0.7 eV in KCl and 0.94 eV in KBr, are predicted, but have not been seen experimentally.     

Interlaboratory Evaluation of Ultraviolet Radiation Emissions from Compact Fluorescent Lamps

There have been many recent reports regarding the potential risks of UV emissions from compact fluorescent lamps (CFLs). In some of these reports, the robustness of the measurements was difficult to discern. We conducted round‐robin measurements, involving three lamp manufacturers and two government research laboratories to gather reliable data on the UV emissions from commercially available CFLs. The initial sample of lamps consisted of 71 spiral‐shaped CFLs purchased from local retailers. From the initial sample, 14 “high UV emitting” CFLs were chosen for further evaluation. We compared the UV emissions at a distance of 20 cm with the UV exposure limits (ELs) published by the International Commission on Non‐ionizing Radiation Protection (ICNIRP). We found that the allowable exposure time for measured lamps ranged from 21 to 415 h. This indicates that the emissions would not exceed the short‐term ELs that have been established by the ICNIRP for healthy individuals. We also evaluated the potential long‐term risk and found it to be insignificant. There was a large variation in the UV emissions found, even for lamps from a single package, indicating that it is impossible to predict the UV output of a CFL based on its physical appearance and model designation.     

Group 4 transition metal CH2=MF2, CHF=MF2, and HC/MF3 complexes formed by C-F activation and alpha-fluorine transfer

Group 4 transition metal methylidene difluoride complexes (CH2=MF2) are formed by the reaction of methylene fluoride with laser-ablated metal atoms and are isolated in an argon matrix. Isotopic substitution of the CH2F2 precursor and theoretical computations (B3LYP and CCSD) confirm product identifications and assignments. Our calculations indicate that the CH2=MF2 complexes have near C2v symmetry and are considerably more stable than other possible products (CH2(mu-F)MF and CHF=MHF). The primary reaction exothermicity provides more than enough energy to activate the initial bridge-bonded CH2(mu-F)MF products on the triplet potential energy surface to complete an alpha-F transfer to form the very stable CH2=MF2 products. Analogous experiments with CHF3 produce CHF=TiF2, which is not distorted at the C-H bond, whereas the heavier group 4 metals form lower-energy triplet HC/MF3 complexes, which contain weak degenerate C(p)-M(d) pi-bonding interactions. Comparisons are made with the CH2=MHF methylidene species, which showed considerable agostic distortions.     

Coordination chemistry of H2 and N2 in aqueous solution. Reactivity and mechanistic studies using trans-FeII(P2)2X2)-type complexes (P2 = a chelating, water-solubilizing phosphine)

The reactions of the trans-Fe(DMeOPrPE)2Cl2 complex (I; DMeOPrPE = 1,2-bis(bis(methoxypropyl)phosphino)ethane) and its derivatives were studied in aqueous and nonaqueous solvents with a particular emphasis on the binding and activation of H2 and N2. The results show there are distinct differences in the reaction pathways between aqueous and nonaqueous solvents. In water, I immediately reacts to form trans-Fe(DMeOPrPE)2(H2O)Cl+. Subsequent reaction with H2 or N2 yields trans-Fe(DMeOPrPE)2(X2)Cl+ (X2=H2 or N2). In the case of H2, further reactivity occurs to ultimately give the trans-Fe(DMeOPrPE)2(H2)H+ product (III). The pathway for the reaction I --> III was spectroscopically examined: following the initial loss of chloride and replacement with H2, heterolysis of the H2 ligand occurs to form Fe(DMeOPrPE)2(H)Cl; substitution of the remaining chloride ligand by another H2 molecule then occurs to produce trans-Fe(DMeOPrPE)2(H2)H+. In the absence of H2 or N2, trans-Fe(DMeOPrPE)2(H2O)Cl+ slowly reacts in water to form Fe(DMeOPrPE)32+, II. Experiments showed that this species forms by reaction of free DMeOPrPE ligand with trans-Fe(DMeOPrPE)2(H2O)Cl+, where the free DMeOPrPE ligand comes from dissociation from the trans-Fe(DMeOPrPE)2(H2O)Cl+ complex. In nonaqueous solvents, the chloride ligand in I is not labile, and a reaction with H2 only occurs if a chloride abstracting reagent is present. Complex III is a useful synthon for the formation of other water-soluble metal hydrides. For example, the trans-[Fe(DMeOPrPE)2H(N2)]+ complex was generated in H2O by substitution of N2 for the H2 ligand in III. The trans-Fe(DHBuPE)2HCl complex (DHBuPE = 1,2-bis(bis(hydroxybutyl)phosphino)ethane, another water-solubilizing phosphine) was shown to be a viable absorbent for the separation of N2 from CH4 in a pressure swing scheme. X-ray crystallographic analysis of II is the first crystal structure report of a homoleptic tris chelate of FeII containing bidentate phosphine ligands. The structure reveals severe steric crowding at the Fe center.     

Bimodal swelling responses in microgel thin films

A series of studies on microgel thin films is described, wherein quartz crystal microgravimetry (QCM), surface plasmon resonance (SPR), and atomic force microscopy (AFM) have been used to probe the properties of microstructured polymer thin films as a function of film architecture and solution pH. Thin films composed of pNIPAm-co-AAc microgels were constructed by using spin-coating layer-by-layer (scLbL) assembly with poly(allylamine hydrochloride) (PAH) as a polycationic "glue". Our findings suggest that the interaction between the negatively charged microgels and the positively charged PAH has a significant impact on the pH responsivity of the film. These effects are observable in both the optical and mechanical behaviors of the films. The most significant changes in behavior are observed when the motional resistance of a quartz oscillator is monitored via QCM experiments. Slight changes to the film architecture and alternating the pH of the environment significantly changes the QCM and SPR responses, suggesting a pH-dependent swelling that is dependent on both particle swelling and polyelectrolyte de-complexation. Together, these studies allow for a deeper understanding of the morphological changes that take place in environmentally responsive microgel-based thin films.     

Tunable Encapsulation of Proteins within Charged Microgels

The binding of cytochrome c to pH and thermoresponsive colloidal hydrogels was investigated using multiangle light scattering, measuring loading through changes in particle molar mass and root mean square radius. Loosely cross-linked microgels [composed of a random copolymer of N-isopropylacrylamide (NIPAm) and acrylic acid (AAc)] demonstrated a high loading capacity for protein. Encapsulation was dependent on both the charge characteristics of the network and the salinity of the medium. Under favorable binding conditions (neutral pH, low ionic strength), microgels containing the highest studied charge density (30 mol% AAc) were capable of encapsulating greater than 9.7 × 10(5) cytochrome c molecules per particle. Binding resulted in the formation of a polymer-protein complex and condensation of the polymer. Anionic microgels demonstrated a change in density ~20-fold in the presence of oppositely charged proteins. These studies of cytochrome c encapsulation represent a significant step towards direct measurement of encapsulation efficiency in complex media as we pursue responsive nanogels and microgels for the delivery of macromolecular therapeutic agents.     

Gold nanoparticles reinforce self-healing microgel multilayers

We report on the finding that absorption of citrate-stabilized Au nanoparticles into microgel/polyelectrolye multilayer thin films results in an increase in the resistance of those films to strain-induced damage in the dry state while maintaining the remarkable self-healing properties of the films following rehydration. Films were fabricated atop elastomeric poly(dimethylsiloxane) substrates by a centrifuge-assisted layer-by-layer technique using anionic hydrogel microparticles (microgels) and cationic linear polymers as the building blocks. Gold nanoparticles were embedded into swollen hydrogel films by a simple immersion method wherein the Coulombic interactions between the anionic Au particles and the polycation are likely important. After drying, the mechanical properties of films were inferred from the observation of cracks/wrinkles formed during stretching of the elastomeric substrate. As-prepared (no Au) hydrogel films revealed the presence of damage perpendicular to the stretching direction (10% strain), as observed previously. However, Au nanoparticle-doped films displayed significantly reduced damage under identical stretching conditions while forming cracks and wrinkles under higher strains (20?C30%). Importantly, all films displayed excellent self-healing behavior upon rehydration regardless of Au content, suggesting that the nanoparticle toughening effect does not interfere with the film mobility required to achieve autonomic repair.     

Gas-phase structures of neutral silicon clusters

Vibrational spectra of neutral silicon clusters Si(n), in the size range of n = 6-10 and for n = 15, have been measured in the gas phase by two fundamentally different IR spectroscopic methods. Silicon clusters composed of 8, 9, and 15 atoms have been studied by IR multiple photon dissociation spectroscopy of a cluster-xenon complex, while clusters containing 6, 7, 9, and 10 atoms have been studied by a tunable IR-UV two-color ionization scheme. Comparison of both methods is possible for the Si(9) cluster. By using density functional theory, an identification of the experimentally observed neutral cluster structures is possible, and the effect of charge on the structure of neutrals and cations, which have been previously studied via IR multiple photon dissociation, can be investigated. Whereas the structures of small clusters are based on bipyramidal motifs, a trigonal prism as central unit is found in larger clusters. Bond weakening due to the loss of an electron leads to a major structural change between neutral and cationic Si(8).     

Quantum Hall ferromagnetism in a two-valley strained Si quantum well

Tilted field magnetotransport study was performed in a two-valley strained Si quantum well and hysteretic diagonal resistance spikes were observed near the coincidence angles. The spike around filling factor ν=3 develops into a giant feature when it moves to the high-field edge of the quantum Hall (QH) state and quenches for higher tilt angles. When the spike is most prominent, its peak resistance is temperature independent from T20 mK up to 0.3 K, which is different from the critical behavior previously reported near the Curie temperature of the QH ferromagnet in AlAs quantum wells. Our data suggest a strong interplay between spins and valleys near the coincidence.