Solution behaviour of lead(II) carboxylates in organic solvents

The solution behaviour has been studied of a series of even chain length lead(II) carboxylates (octanoate to octadecanoate) and the odd chain length lead(II) heptadecanoate in a variety of non-complexing organic solvents and in alcohols. In agreement with previous studies, solubility increases dramatically above a certain temperature, which depends on solute concentration, chain length and solvent. This solution temperature is also affected by traces of water. These results are complemented by studies using vapour pressure osmometry, dynamic light scattering, ¹H and ¹³NMR spectroscopy. The results in water-free systems are consistent with the formation of rather ill-defined, polydisperse aggregates, which increase in size with concentration and decrease with temperature. These show similar local structure to lamellar mesophases in the pure lead(II) carboxylates, and are suggested to be formed by solvent induced swelling and break-up of these mesophases. In the presence of water, a more ordered structure is formed, in which a few water molecules are suggested to be bound to the lead(II) carboxylate headgroup.     

New High-Resolution Analysis of the nu(3) Band of the (15)N(16)O(2) Isotopomer of Nitrogen Dioxide by Fourier Transform Spectroscopy

New high-resolution Fourier transform absorption spectra of an (15)N(16)O(2) isotopic sample of nitrogen dioxide were recorded at the University of Bremen in the 6.3-μm region. Starting from the results of a previous study [Y. Hamada, J. Mol. Struct. 242, 367-377 (1991)], a new and more extended analysis of the nu(3) band located at 1582.1039 cm(-1) has been performed. The spin-rotation energy levels were satisfactorily reproduced using a theoretical model which takes into account both the Coriolis interactions between the spin-rotation energy levels of the (001) vibrational state with those of the (020) and (100) states and the spin-rotation resonances within each of the NO(2) vibrational states. Precise vibrational energies and rotational, spin-rotation, and coupling constants were obtained in this way for the first triad of (15)N(16)O(2) interacting states {(020), (100), (001)}. Finally, a comprehensive list of line positions and line intensities of the {nu(1), 2nu(2), nu(3)} interacting bands of (15)N(16)O(2) was generated, using for the line intensities the transition moment operators which were obtained previously for the main isotopic species. Copyright 2000 Academic Press.     

Electrophysiological evidence for the critical band in humans: middle-latency responses

Electrophysiological evidence for the critical band phenomenon in humans using event-related potentials has been sought for many years with conflicting results. Components Na and Pa of the middle-latency response (MLR) and wave V of the auditory brain-stem response (ABR) were simultaneously recorded in response to a two-tone complex varying in bandwidth from 76 Hz to 1012 Hz, centered at 2 kHz, and presented at an overall level of 85 dB SPL, in ten normal female subjects. Only the amplitude of Na showed an abrupt increase as bandwidth changed from 268 to 330 Hz, yielding an estimate of critical bandwidth in good agreement with previous behavioral estimates.     

Room temperature rate coefficient for the reaction between CH3O2 and NO3

The molecular modulation spectroscopic technique was employed to study the kinetics of NO₃ radicals produced in the 253.7 nm photolysis of flowing gas mixtures of HNO₃/CH₄/O₂ at room temperature. By computer fitting of the NO₃ temporal behavior, a rate coefficient of (2.3 ± 0.7) × 10^?12 cm³ molecule^?1 s^?1 was obtained for the reaction between NO₃ and CH₃O₂ at 298 K.     

Improved direct measurement of A(b) and A(c) at the Z(0) pole using a lepton tag

The parity violation parameters A(b) and A(c) of the Zb(b) and Zc(c) couplings have been measured directly, using the polar angle dependence of the polarized cross sections at the Z(0) pole. Bottom and charmed hadrons were tagged via their semileptonic decays. Both the electron and muon analyses take advantage of new multivariate techniques to increase the analyzing power. Based on the 1993-1998 SLD sample of 550,000 Z(0) decays produced with highly polarized electron beams, we measure A(b) = 0.919+/-0.030(stat)+/-0.024(syst), and A(c) = 0.583+/-0.055(stat)+/-0.055(syst).     

Electroluminescent zinc(II) bis(8-hydroxyquinoline): structural effects on electronic states and device performance

We present direct evidence for stable oligomers in vacuum-deposited thin films of zinc(II) bis(8-hydroxyquinoline) (Znq(2)). The tetramer [(Znq(2))(4)] is the energetically favored configuration in both the single crystal and the vacuum-deposited thin film. Oligomerization leads to distinct, symmetry-driven differences between the electronic states in Znq(2) and those in the archetypal organic electroluminescent molecule tris(8-hydroxyquinoline) aluminum (Alq(3)). In the case of the Znq(2) tetramer, symmetry leads to an extended network of overlapping pyridyl and phenolato moieties in the solid film. Analysis of the electronic structure of (Znq(2))(4) calculated by ab initio Hartree-Fock (HF) methods reveals a localization and energy shift of high-lying occupied and low-lying unoccupied states on symmetry related ligands located on opposite sides of the supramolecular structure resulting in a dipole moment for (Znq(2))(4) tetramer close to zero. The optimal pi-overlap pathways, altered charge distributions, and extended electronic states of tetrameric Znq(2) may be expected to enable low operating voltage organic light-emitting devices (OLEDs) based on Znq(2). We present preliminary evidence that the operating voltage of (Znq(2))(4)-based OLEDs is indeed lower than that of identical devices made with Alq(3). Strategic substitution of 8-hydroxyquinoline ligands and control of the structural symmetry of the corresponding metal chelates may offer a route to high efficiency and low operating voltage small molecule OLEDs.