Vibrational spectroscopy of triacetone triperoxide (TATP): anharmonic fundamentals, overtones and combination bands

The vibrational spectrum of triacetone triperoxide (TATP) is studied by the correlation-corrected vibrational self-consistent field (CC-VSCF) method which incorporates anharmonic effects. Fundamental, overtone, and combination band frequencies are obtained by using a potential based on the PM3 method and yielding the same harmonic frequencies as DFT/cc-pVDZ calculations. Fundamentals and overtones are also studied with anharmonic single-mode (without coupling) DFT/cc-pVDZ calculations. Average deviations from experiment are similar for all methods: 2.1-2.5%. Groups of degenerate vibrations form regions of numerous combination bands with low intensity: the 5600-5800 cm(-1) region contains ca. 70 overtones and combinations of CH stretches. Anharmonic interactions are analyzed.     

Dynamics of proton recombination with NO3- anion in water clusters

Recombination events of a proton with NO3- at (H2O)8 clusters are studied by molecular dynamics, using "on-the-fly" reliable ab initio MP2 potentials. The main findings are: (1) the lifetime of the ions is less than 1.2 picoseconds; (2) the recombination step invariably involves H3O+, not H5O2+; and (3) an essentially unique transition-state structure of H3O+/NO3- for recombination is found in all cases. Proton migration involves both H3O+ and H5O2+ species: Grotthuss and other mechanisms contribute.     

A small neutral molecule with two noble-gas atoms: HXeOXeH

A novel noble-gas compound, HXeOXeH, is identified using IR spectroscopy, and it seems to be the smallest known neutral molecule with two noble-gas atoms. HXeOXeH is prepared using, for example, UV photolysis of water in solid xenon and subsequent annealing at 40-45 K. The experimental observations are fully supported by extensive quantum chemical calculations. A large energy release of 8.3 eV is computationally predicted for the decomposition of HXeOXeH into the 2Xe + H2O global energy minimum. HXeOXeH may represent a first step toward the possible preparation of (Xe-O)n chains and it may be relevant to the terrestrial "missing xenon" problem.     

Determination of free and reversibly-bound sulfite in selected foods by high-performance liquid chromatography with fluorometric detection

A rapid and accurate method for measuring low part-per-million levels of free and reversibly-bound sulfites in selected foods by using high-performance liquid chromatography (HPLC) with fluorometric detection was developed. Sulfites were extracted with sodium tetrachloromercurate solution and determined by HPLC-fluorescence spectrometry. During the HPLC analysis, the sample extract was reacted with sodium hydroxide to liberate the reversibly-bound sulfite and subsequently separated from other interferences by a size exclusion column. The effluent was then reacted with o-phthalaldehydelammonium chloride reagent to form a fluorescing 1-sulfonatoisoindole derivative and analyzed by a fluorescence detector. The method has been applied to a variety of foods and food products, with no significant interference encountered in matrixes such as soy products, cabbage, broccoli, brassica, ginger, fungus, mushroom, mandarin peel, potato chips, and biscuits. It was shown to have a broad linear range of 0.01 to 0.4 mg/L as SO2. The spike recoveries of sodium sulfite, sodium metabisulfite, and formaldehyde-sodium bisulfite adduct at the 5 to 10 mg/kg level in the tested food matrix were within 80-120%, and the limit of detection was 5 mg/kg. Laboratory of Government Chemist Reference Material LGC7111 (potato powder) was used to assess the accuracy of the method. The expanded measurement uncertainty of the method at 95% confidence level was estimated to be 17%.     

On a conjecture of Erdős and Simonovits: Even cycles

Let F be a family of graphs. A graph is F-free if it contains no copy of a graph in F as a subgraph. A cornerstone of extremal graph theory is the study of the Turán number ex(n,F), the maximum number of edges in an F-free graph on n vertices. Define the Zarankiewicz number z(n,F) to be the maximum number of edges in an F-free bipartite graph on n vertices. Let C _k denote a cycle of length k, and let C _k denote the set of cycles C _?, where 3≤?≤k and ? and k have the same parity. Erd?s and Simonovits conjectured that for any family F consisting of bipartite graphs there exists an odd integer k such that ex(n,F ∪ C _k ) ～ z(n,F) — here we write f(n) ～ g(n) for functions f,g: ? → ? if lim _n→∞ f(n)/g(n)=1. They proved this when F ={C ₄} by showing that ex(n,{C ₄;C ₅})～z(n,C ₄). In this paper, we extend this result by showing that if ?∈{2,3,5} and k>2? is odd, then ex(n,C _2? ∪{C _k }) ～ z(n,C _2? ). Furthermore, if k>2?+2 is odd, then for infinitely many n we show that the extremal C _2? ∪{C _k }-free graphs are bipartite incidence graphs of generalized polygons. We observe that this exact result does not hold for any odd k<2?, and furthermore the asymptotic result does not hold when (?,k) is (3, 3), (5, 3) or (5, 5). Our proofs make use of pseudorandomness properties of nearly extremal graphs that are of independent interest.     

Numerical modeling of the receptivity of a supersonic boundary layer to acoustic disturbances

The receptivity of a supersonic (M_∞ = 6) boundary layer on a flat plate to acoustic disturbances is investigated on the basis of a numerical solution of the 2D Navier-Stokes equations. Numerical results obtained for fast and slow acoustic waves impinging on the plate at zero angle agree qualitatively with asymptotic theory. Calculations carried out for other angles of incidence of the acoustic waves reveal new features of the perturbation field in the neighborhood of the leading edge of the plate. It is shown that, due to visco-inviscid interaction, the shock formed near the leading edge may significantly affect the acoustic field and the receptivity.     

Time-dependent strength of colloidal gels

Colloidal silica gels are shown to stiffen with time, as demonstrated by both dynamic light scattering and bulk rheological measurements. Their elastic moduli increase as a power law with time, independent of particle volume fraction; however, static light scattering indicates that there are no large-scale structural changes. We propose that increases in local elasticity arising from bonding between neighboring colloidal particles can account for the strengthening of the network, while preserving network structure.     

Spectrum of charged particle oscillations in an RF quadrupole field

Variations in the spectral composition of ion oscillations within several stability regions of a quadrupole mass filter were studied. The frequency spectrum was shown to consist of two line systems. Side lines ω_n=nω₀±βω₀/2 were observed in the oscillation spectrum near harmonics nω₀ (n=0, 1, 2,...), where ω₀ is the circular frequency of an RF field and β is the stability parameter. Near the boundaries of the stability regions, the oscillations took the form of beatings. For even values of the stability parameter, β=2k (k=1, 2,...), the beat frequency coincides with the fundamental frequency ω₀ and, for β=2k−1, the main beat frequencies are ω₀/2 and 3ω₀/2.