Photochemical processes induced by 157-nm light in H(2)-impregnated glassy SiO(2):OH

F(2) excimer-laser irradiation induces two major changes in SiO(2): OH glass impregnated with H(2) molecules. First, the vacuum-UV optical absorption edge is bleached, and the absorption at 157 nm decreases from 0.95 to 0.68 cm(-1) . Second, preexisting free SiOH groups and interstitial H(2) are photochemically converted to hydrogen-bonded hydroxyl groups. It is suggested that the bleaching of the UV-absorption edge is caused by a change of OH groups from a free to a hydrogen-bonded state and by photolysis of distorted Si-O bonds that are absorbing in the edge region.     

Effect of randomness on the ESR hyperfine structure of Cd+

The ESR spectra of the 5s¹ state of Cd⁺, induced with gamma-ray irradiation, were measured for polycrystalline CaO, β-Ca(PO₃)₂ and glassy Ca(PO₃)₂ matrices. It has been found out that one of the hyperfine absorptions due to the magnetic nuclei (¹¹¹Cd and ¹¹³Cd) reflects very senstively the structural fluctuation around the center in terms of pronounced line broadening. Such a feature was explained reasonably well by introducing the distribution of the hyperfine coupling constant. It was emphasized that Cd²⁺, the precursor of Cd⁺, is a very suitable probe to study the local randomness around Ca²⁺ in solids.     

Electron localization and a confined electron gas in nanoporous inorganic electrides

The nanoporous main group oxide 12CaO.7Al(2)O3 (C12A7) can be transformed from a wide-gap insulator to an electride where electrons substitute anions in cages constituting a positive frame. Our ab initio calculations of the electronic structure of this novel material give a consistent explanation of its high conductivity and optical properties. They show that the electrons confined in the inert positive frame are localized in cages and undergo hopping between neighboring cages. The results are useful for the understanding of behavior of confined electron gas of different topology and electron-phonon coupling, and for designing new transparent conductors, electron emitters, and electrides.     

Chirped-pulse amplification of ultraviolet femtosecond pulses by use of Ce(3+):LiCaAlF(6) as a broadband, solid-state gain medium

Chirped-pulse amplification in the ultraviolet region is demonstrated by use of a broadband Ce(3+): LiCaAlF(6) laser medium. A modified bow-tie-style four-pass amplifier pumped by 100-mJ, 266-nm pulses from a Q -switched Nd:YAG laser has a gain factor of 370 and delivers 6-mJ, 290-nm pulses. After dispersion compensation, the output pulses can be compressed to 115 fs.     

Dimensions of branched polymers formed in simultaneous long‐chain branching and random scission

In free‐radical olefin polymerizations, the polymer‐transfer reactions could lead to chain scission as well as the formation of long‐chain branches. The Monte Carlo simulation for free‐radical polymerization that involves simultaneous long‐chain branching and random scission is used to investigate detailed branched structure. The relationship between the mean‐square radius of gyration 〈s²〉 and degree of polymerization P as well as that between the branching density and P is the same for both with and without random scission reactions—at least for smaller frequencies of scission reactions. The 〈s²〉 values were larger than those calculated from the Zimm–Stockmayer (Z‐S) equation in which random distribution of branch points is assumed, and therefore, the Z‐S equation may not be applied for low‐density polyethylenes. The elution curves of size exclusion chromatography were also simulated. The molecular weight distribution (MWD) calibrated relative to standard linear polymers is much narrower than the true MWD, and high molecular weight tails are clearly underestimated. A simplified method to estimate the true MWD from the calibrated MWD data is proposed. The MWD obtained with a light scattering photometer in which the absolute weight‐average molecular weight of polymers at each retention volume is determined directly is considered a reasonable estimate of the true MWD. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2960–2968, 2001     

Metallocene bis(perfluoroalkanesulfonate)s as air-stable cationic Lewis acids

Zirconocene and titanocene bis(perfluorooctanesulfonate)s were synthesized. In contrast to the corresponding triflates and perchlorates, these compounds are air- and water-stable. They were proved to be ionic on the basis of conductivity measurements and X-ray analysis, allowing these complexes to be stored for months. The strong Lewis acidity of these cationic metallocene species, which was proved by ESR study, enabled catalytic glycosylation.     

Origins of hole doping and relevant optoelectronic properties of wide gap p-type semiconductor, LaCuOSe

LaCuOSe is a wide band gap (～2.8 eV) semiconductor with unique optoelectronic properties, including room-temperature stable excitons, high hole mobility ～8 cm(2)/(Vs), and the capability of high-density hole doping (up to 1.7 × 10(21) cm(-3) using Mg). Moreover, its carrier transport and doping behaviors exhibit nonconventional results, e.g., the hole concentration increases with decreasing temperature and the high hole doping does not correlate with other properties such as optical absorption. Herein, secondary ion mass spectroscopy and photoemission spectroscopy reveal that aliovalent ion substitution of Mg at the La site is not the main source of hole doping and the Fermi level does not shift even in heavily doped LaCuOSe:Mg. As the hole concentration increases, the subgap optical absorption becomes more intense, but the increase in intensity does not correlate quantitatively. Transmission electron microscopy indicates that planar defects composed of Cu and Se deficiencies are easily created in LaCuOSe. These observations can be explained via the existence of a degenerate low-mobility layer and formation of complex Cu and Se vacancy defects with the assistance of generalized gradient approximation band calculations.     

Allosteric effect of the first lead ion on stepwise extraction of the second lead ion with p-t-butylcalix[5]arene pentacarboxylic acid derivative

A calix[5]arene-based solvent extraction reagent displaying very high selectivity for lead has been prepared, one molecule of which extracts two lead ions in a stepwise manner. The first Pb²⁺ ion is bound to five phenoxy oxygen atoms inside the calixarene cavity due to which the ligand undergoes conformational freezing in stable cone conformer. This causes positive allosteric effect for co-extraction of the second lead ion due to the aggregation of functional groups.     

Pure red electrophosphorescence from polymer light-emitting diodes doped with highly emissive bis-cyclometalated iridium(III) complexes

In order to develop highly emissive red phosphorescent materials for OLED application, novel bis-cyclometalated iridium(III) complexes were developed using the 1-(dibenzo[b,d]furan-4-yl)isoquinolinato-N,C^3′ (dbfiq) cyclometalating ligand. When 1,3-bis(3,4-dibutoxyphenyl)propane-1,3-dionate (bdbp) is employed as an ancillary ligand, Ir(dbfiq)₂(bdbp) 1 exhibits red photoluminescence (PL) at 640 nm with a quantum yield (Φ_PL) of 0.61 (in toluene, 298 K). Replacement of bdbp to dipivaloylmethanate (dpm) and acetylacetonate (acac) (Ir(dbfiq)₂(dpm) 2 and Ir(dbfiq)₂(acac) 3, respectively) does not affect the PL spectrum, but reduces Φ_PL to 0.55 and 0.49 for 2 and 3, respectively. Similar tendency is also found in the doped poly(methyl methacrylate) (PMMA) film, and 1 is more emissive (Φ_PL = 0.17) than 2 and 3 (Φ_PL = 0.08 and 0.06, respectively). Using 1 as a phosphorescent dopant, polymer light-emitting diodes (PLEDs) were fabricated, of which structure was ITO/PEDOT:PSS (40 nm)/PVCz:1:PBD (100 nm)/CsF (1 nm)/Al (250 nm). Pure red electroluminescence (EL) is obtained from the fabricated PLEDs, affording a CIE chromaticity coordinate of (0.68, 0.31). When 0.51 mol% of 1 is incorporated in the PVCz-based emitting layer, the PLED shows maximum luminance of 7270 cd m⁻² at 16.5 V, power efficiency of 1.4 lm W⁻¹ at 7.5 V, and external quantum efficiency of 6.4% at 9.0 V. PLEDs with the same structure and components were also fabricated using 2 and 3, and their device characteristics were investigated. In proportion to the PL quantum yields, 1 affords better device performance than 2 and 3. Owing to four butoxy groups introduced to the bdbp ligand, 1 exhibits high solubility in organic solvents such as chloroform and toluene, and thus, is an excellent red phosphorescent dopant for solution-processed OLEDs.     

On Subordination Chains with Normalization Given by a Time-dependent Linear Operator

In this paper we are concerned with solutions, in particular with univalent solutions, of the Loewner differential equation associated with non-normalized subordination chains on the Euclidean unit ball B ⁿ in \mathbbCⁿ{\mathbb{C}^n}. The main result is a generalization to higher dimensions of a well known result due to Becker. Various particular cases of this result have been recently obtained for subordination chains with normalization Df(0,t)=e^tI_n{Df(0,t)=e^tI_n} or Df(0, t) = e ^tA , t ≥ 0, where A ? L(\mathbbCⁿ,\mathbbCⁿ){A\in L(\mathbb{C}^n,\mathbb{C}^n)}. We also determine the form of the standard solutions to the Loewner differential equation associated with generalized spirallike mappings. In the last section we obtain the form of the solution in the presence of coefficient bounds.