Sorptive reconstruction of the CuAlCl(4) framework upon reversible ethylene binding

Three ethylene adducts to CuAlCl(4) have been characterized by single crystal and/or powder X-ray diffraction, (13)C, (27)Al and (63)Cu MAS NMR and diffuse reflectance UV-vis spectroscopy. (C(2)H(4))(2)CuAlCl(4), a = 7.1274(5) b = 12.509(1) c = 11.997(3) beta = 91.19 degrees, Pc, Z = 4; alpha-(C(2)H(4))CuAlCl(4), a =7.041(3) b = 10.754(8) c =11.742(9) beta = 102.48(6), P2(1), Z = 4 and beta-(C(2)H(4))CuAlCl(4), a = 7.306(2), b = 16.133(3), c = 7.094(1), Pna2(1), Z = 4. Up to 2 equiv of ethylene ( approximately 200 cm(3)/g relative to stp) are sorbed at room temperatures and pressures as low as 300 Torr. The ethylene ligands are bound to copper (I) primarily through a sigma-interaction, because the AlCl(4)(-) groups also bound to copper prevent any significant pi-back-bonding. The olefin binding is reversible and has been characterized by gravimetric and volumetric adsorption analysis and by time and pressure resolved synchrotron powder X-ray diffraction. Comparison of the parent crystal structure to those of the adduct phases provide an atomistic picture of the sorptive reconstruction reactions. These are proposed to proceed by a classic substitution mechanism that is directed by the van der Waals channels of the parent crystalline lattice.     

Aspects of retention behaviour of steroids in packed column supercritical fluid chromatography

Summary A selection of steroids of different polarities and different polar functional groups was investigated in terms of retention and elution profile. It was found that the apparent polarity of steroids is determined not only by the amount and the nature of polar functional groups but also by their intramolecular interactions, shielding effects and molecular shape due to the conformation of the molecule.     

Algebraic decay in self-similar Markov chains

A continuous-time Markov chain is used to model motion in the neighborhood of a critical invariant circle for a Hamiltonian map. States in the infinite chain represent successive rational approximants to the frequency of the invariant circle. For the case of a noble frequency, the chain is self-similar and the nonlinear integral equation for the first passage time distribution is solved exactly. The asymptotic distribution is a power law times a function periodic in the logarithm of the time. For parameters relevant to the critical noble circle, the decay proceeds ast ^–4.05.     

Degrees and matchings

Let n, b, d be positive integers. We evaluate f(n, b, d), the largest possible number of edges in a graph with n vertices having no vertex of degree greater than d and no set of more than b independent edges. Our proof technique has a linear programming flavor and uses Berge's matching formula.     

Solid state NMR spectroscopy of metal carbonyls. The influence of site symmetry on the solid state spectrum of cis-(η5-C5H5)2Fe2(CO)4

Solid state carbon-13 NMR spectra of metal carbonyls are readily obtained using commercial instrumentation. The observed isotropic chemical shifts are in good agreement with solution values. Furthermore there is a one-to-one correspondence between crystallographically unique carbonyls and magnetically distinguishable carbonyls in the absence of accidental degeneracies. For cis-(η⁵-C₅H₅)₂Fe₂(CO)₄ the site symmetry is C₁ while the molecular symmetry is C_2ν. The lower solid state symmetry gives rise to more resonances in the solid spectrum than in solution. Magic angle tuning and chemical shifts were obtained using hexamethylbenzene as a standard.     

D meson production and decay in e+e− annihilation at 4.03 and 4 GeV c.m. energy

Decay modes of the charmed mesons, D⁰ and D⁺, are studied in e⁺e^? annihilation data at 4.03 and 4.41 GeV c.m. energy. The products of cross section times branching ratio are measured for the K^?π⁺, K^?π⁺π⁺π^?, K_Sπ⁺π^? and K^?π⁺π⁺ final states. Upper limits are established for the Cabibbo forbidden decays via π⁺π^?, K⁺K^?, K⁺K^? π⁺, K⁺π⁺π^? and π⁺π^?π⁺. The K^?π⁺π⁺π^? final state is shown to be dominated by K^?π⁺ρ⁰.     

Wavelength modulation absorption spectroscopy with 2 f detection using multiplexed diode lasers for rapid temperature measurements in gaseous flows

Multiplexed fiber-coupled diode lasers are used to probe second-harmonic line shapes of two near-infrared water absorption features, at 1343 nm and 1392 nm, in order to infer temperatures in gases containing water vapor, such as combustion flows. Wavelength modulation is performed at 170 kHz, and is superimposed on 1-kHz wavelength scans in order to recover full second-harmonic line shapes. Digital waveform generation and lock-in detection are performed using a data-acquisition card installed in a PC. An optimal selection of the modulation indices is shown to greatly simplify data interpretation over extended temperature ranges and to minimize the need for calibration when performing 2 f ratio thermometry. A theoretical discussion of this optimized strategy for 2 f ratio thermometry, as well as results from experimental validations in a heated cell, at pressures up to atmospheric, are presented in order to illustrate the utility of this technique for rapid temperature measurements in gaseous flow fields. PACS 42.62.Fi; 42.55.Px; 42.60.Fc; 39.30.+w     

OPTIMAL HARVESTING WITH DENSITY DEPENDENT RANDOM EFFECTS

We consider the effect of sudden large, randomly occurring density dependent disasters on the optimal harvest policy and optimal expected return for an exploited population. The population is assumed to grow logistically with disasters occurring on a time scale very short compared to the natural growth scale. The case of a density dependent disaster frequency is also treated. Stochastic dynamic programming is used in the optimization. For a set of realistic field data it is found that random effects typically have a significant effect on both optimal return and optimal effort levels. The effect of density dependence is far more pronounced for optimal return than for optimal effort levels.