Spectroscopic studies of ionic solvation. XVIII. Solvation of the lithium ion in acetone and acetone-nitromethane mixtures

Solvation of the lithium ion by acetone was studied in acetone-nitromethane solutions by Raman, infrared, and⁷Li and³⁵Cl NMR spectroscopic techniques. It was confirmed that the 390-cm^?1 IR acetone band is split by the lithium ion and that a 369-cm^?1 IR band, attributed by other authors to Li⁺-nitromethane vibration, is due to the vibration of acetone in the lithium inner solvation shell. The frequency of the Li⁺-nitromethane vibrational band is strongly anion dependent due to contact-ion-pair formation. Several different techniques indicate that Li⁺ is solvated by four acetone molecules, and approximate equilibrium-constant values for the stepwise solvation reaction were calculated. The influence of weak complexing agents on Li⁺ ClO ₄ ^? ion-pair formation was investigated.     

Photochemistry of refractive index structures in poly(methyl methacrylate) by femtosecond laser irradiation

Femtosecond, subablation threshold photomodification of poly(methyl methacrylate) (PMMA) at 387 nm is explored to enable fabrication of optical components. Volatile fragment analysis (thermal desorption gas chromatography-mass spectrometry) and molecular weight distribution monitoring (size exclusion chromatography) suggest photochemical modification, involving direct cleavage of the polymer backbone and propagation via chain unzipping under formation of monomers, similar to the pyrolytic degradation of PMMA. Waveguides were produced in undoped, clinical-grade PMMA, showing an increased refractive index in the laser focal region (Dnmax=4x10(-3)).     

Acoustic analyses and perceptual data on anticipatory labial coarticulation in adults and children

The present study investigated anticipatory labial coarticulation in the speech of adults and children. CV syllables, composed of [s], [t], and [d] before [i] and [u], were produced by four adult speakers and eight child speakers aged 3-7 years. Each stimulus was computer edited to include only the aperiodic portion of fricative-vowel and stop-vowel syllables. LPC spectra were then computed for each excised segment. Analyses of the effect of the following vowel on the spectral peak associated with the second formant frequency and on the characteristic spectral prominence for each consonant were performed. Perceptual data were obtained by presenting the aperiodic consonantal segments to subjects who were instructed to identify the following vowel as [i] or [u]. Both the acoustic and the perceptual data show strong coarticulatory effects for the adults and comparable, although less consistent, coarticulation in the speech stimuli of the children. The results are discussed in terms of the articulatory and perceptual aspects of coarticulation in language learning.     

A computational study of substituent effects on the stability and geometry of carbazole‐pyridine complexes

Hydrogen bonding between carbazole and pyridine is known to quench fluorescence emission of carbazole. Three carbazolopyridinophanes—compounds composed of carbazole and pyridine subunits such that an intramolecular hydrogen bond may exist between them—have been pursued as reversible fluorescent sensors that detect given analytes through fluorescence restoration. However, these sensors exhibit background fluorescence believed to be related to the proportion of non‐hydrogen‐bonded conformers present. In this computational investigation, the potential energy surfaces of various hydrogen‐bonded carbazole:pyridine complexes are investigated using density functional theory with the intent of explaining the observed background fluorescence for the carbazolopyridinophanes. The results indicate carbazolopyridinophane conformers most resembling the geometry of their corresponding free carbazole:pyridine complexes exhibit the least background fluorescence.     

Adaptive unstructured finite element method for two-dimensional detonation simulations

A non-equilibrium reacting flow methodology has been added to a conservative, monotonic, compressible flow solver to allow numerical simulations of gas detonations. This flow solver incorporates unstructured dynamically adaptive meshes with the Finite Element Method – Flux Corrected Transport (FEM-FCT) scheme, which has shown excellent predictive capability of various non-reacting compressible flows. A two-step induction parameter model was used to model the combustion of the gas phase coupled with an energy release equation which was simulated with a point implicit finite element scheme. This combustion model was then applied to a two-dimensional detonation test case of a hypothetical fuel:oxygen mixture. The detonation simulation yielded two transverse waves which continued to propagate. This feature and the detonation shock speed mean and fluctuations were found to be grid-independent based on a resolution of about twenty elements within the average induction length. The resolution was efficiently achieved with the unstructured dynamically adaptive finite elements, which were three orders of magnitude less in number then required for uniform discretization. Received 26 August 1996 / Accepted 31 March 1997     

Spatial No-Waiting Stations with Moving Customers

We analyze spatial MAP/G/∞-, spatial MAP/G/c/0¹ and spatial Cox/G/∞-stations with group arrivals over some Polish space X (with Borel σ-algebra X), including the aspect of customer motion in space. For models with MAP-input, characteristic differential equations are set up that describe the dynamics of phase dependent random functions Q _r;ij (u,t;S′), where Q _r;ij (u,t;S′) is the probability to observe, at time u≤t, the number r of those customers in some source set S′∈X, who will be in a destination set S∈X at time t. For Cox/G/∞-stations, i.e., infinite server stations with doubly stochastic input, the arrival intensities as well as service times may depend on some general stochastic process (J′ _t ) _t≥0 with countable state space. For that case we obtain explicit expressions for space–time distributions as well as stationary and non-stationary characteristics.