Vacuum-Ultraviolet negative photoion spectroscopy of SF5Cl

Using vacuum-UV radiation from a synchrotron, gas-phase negative ions are detected by mass spectrometry following photoexcitation of SF$_5$Cl. F$^-$, Cl$^-$ and SF$_5^-$are observed, and their ion yields recorded in the range 8-30 eV. F$^-$ and Cl$^-$ show a linear dependence of signal with pressure, showing that they arise from unimolecular ion-pair dissociation, generically written AB + h$v$ $\rightarrow$ C$^-$ + D$^+$ (+ neutral(s)). F$^-$ is the strongest signal, and absolute cross sections are determined by calibrating the signal intensity with that of F$^-$ from SF$_6$ and CF$_4$. Resonances are observed, and assigned to transitions to Rydberg states of SF$_5$Cl. The Cl$^-$ signal is much weaker, despite the S-Cl bond being significantly weaker than the S-F bond. Appearance energies for F$^-$ and Cl$^-$ of 12.7 ± 0.2 and 10.6 ± 0.2 eV are determined. The spectra suggest that these ions form indirectly by crossing of Rydberg states of SF$_5$Cl onto an ion-pair continuum

An approximation theorem for nuclear operator systems

We prove that an operator system $\mathcal S$ is nuclear in the category of operator systems if and only if there exist nets of unital completely positive maps \phi_\lambda : \cl S \to M_{n_\lambda} and \psi_\lambda : M_{n_\lambda} \to \cl S such that $\psi_\lambda \circ \phi_\lambda$ converges to {\rm id}_{\cl S} in the point-norm topology. Our proof is independent of the Choi-Effros-Kirchberg characterization of nuclear $C^*$-algebras and yields this characterization as a corollary. We give an example of a nuclear operator system that is not completely order isomorphic to a unital $C^*$-algebra.Comment: 10 pages; to appear in JF

On the determinant bundles of abelian schemes

Let \pi:\CA\ra S be an abelian scheme over a scheme $S$ which is quasi-projective over an affine noetherian scheme and let \CL be a symmetric, rigidified, relatively ample line bundle on \CA. We show that there is an isomorphism \det(\pi_*\CL)^{\o times 24}\simeq\big(\pi_*\omega_{\CA}^{\vee}\big)^{\o times 12d} of line bundles on $S$, where $d$ is the rank of the (locally free) sheaf \pi_*\CL. We also show that the numbers 24 and $12d$ are sharp in the following sense: if $N>1$ is a common divisor of 12 and 24, then there are data as above such that \det(\pi_*\CL)^{\o times (24/N)}\not\simeq\big(\pi_*\omega_{\CA}^{\vee}\big)^{\o times (12d/N)}.Comment: 8 page

Rate constants and Arrhenius parameters for the reactions of OH radicals and Cl atoms with CF3CH2OCHF2, CF3CHClOCHF2 and CF3CH2OCClF2, using the discharge-flow/resonance fluorescence method

Rate constants have been determined for the reactions of OH radicals and Cl atoms with the three partially halogenated methyl-ethyl ethers, CF$_3$CH$_2$OCHF$_2$, CF$_3$CHClOCHF$_2$ and CF$_3$CH$_2$OCClF$_2$, using discharge-flow techniques to generate the OH radicals and the Cl atoms and resonance fluorescence to observe changes in their relative concentrations in the presence of added ether. For each combination of radical and ether, experiments were carried out at three temperatures between 292 and 410 K, yielding the following Arrhenius expressions for the rate constants within this range of temperature: OH + CF$_3$CH$_2$OCHF$_2$: $k$ = (2.0$\pm$0.8) $\times$ 10$^{-11}$ exp( – 2110 $\pm$ 150 K / T) cm$^3$ molecule$^{-1}$ s$^{-1}$ OH + CF$_3$CHClOCHF$_2$: $k$ = (4.5 $\pm$ 1.3) $\times$ 10$^{-13}$ exp( – 940 $\pm$ 100 K / T) cm$^3$ molecule$^{-1}$ s$^{-1}$ OH + CF$_3$CH$_2$OCClF$_2$: $k$ = (1.6 $\pm$ 0.6) $\times$ 10$^{-12}$ exp( – 1100 $\pm$ 125 K / T) cm$^3$ molecule$^{-1}$ s$^{-1}$ Cl + CF$_3$CH$_2$OCHF$_2$: $k$ = (6.1 $\pm$ 1.4) $\times$ 10$^{-12}$ exp( – 1830 $\pm$ 90 K / T) cm$^3$ molecule$^{-1}$ s$^{-1}$ Cl + CF$_3$CHClOCHF$_2$: $k$ = (7.8 $\pm$ 2.6) $\times$ 10$^{-11}$ exp( – 2980 $\pm$ 130 K / T) cm$^3$ molecule$^{-1}$ s$^{-1}$ Cl + CF$_3$CH$_2$OCClF$_2$: $k$ = (2.2 $\pm$ 0.2) $\times$ 10$^{-11}$ exp( – 2700 $\pm$ 40 K / T) cm$^3$ molecule$^{-1}$ s$^{-1}$ The results are compared with those obtained previously for the same and related reactions of OH radicals and Cl atoms, and the atmospheric implications of the results are considered briefly

Orbital Configurations and Magnetic Properties of Double-Layered Antiferromagnet Cs3_3Cu2_2Cl4_4Br3_3

We report the single-crystal X-ray analysis and magnetic properties of a new double-layered perovskite antiferromagnet, Cs$_3$Cu$_2$Cl$_4$Br$_3$. This structure is composed of Cu$_2$Cl$_4$Br$_3$ double layers with elongated CuCl$_4$Br$_2$ octahedra and is closely related to the Sr$_3$Ti$_2$O$_7$ structure. An as-grown crystal has a singlet ground state with a large excitation gap of $\Delta/k_{\rm B}\simeq 2000$ K, due to the strong antiferromagnetic interaction between the two layers. Cs$_3$Cu$_2$Cl$_4$Br$_3$ undergoes a structural phase transition at $T_{\rm s}\simeq330$ K accompanied by changes in the orbital configurations of Cu$^{2+}$ ions. Once a Cs$_3$Cu$_2$Cl$_4$Br$_3$ crystal is heated above $T_{\rm s}$, its magnetic susceptibility obeys the Curie-Weiss law with decreasing temperature even below $T_{\rm s}$ and does not exhibit anomalies at $T_{\rm s}$. This implies that in the heated crystal, the orbital state of the high-temperature phase remains unchanged below $T_{\rm s}$, and thus, this orbital state is the metastable state. The structural phase transition at $T_{\rm s}$ is characterized as an order-disorder transition of Cu$^{2+}$ orbitals.Comment: 6pages. 6figures, to appear in J. Phys. Soc. Jpn. Vol.76 No.

Solvent drag measurement of transcellular and basolateral membrane NaCl reflection coefficient in kidney proximal tubule.

The NaCl reflection coefficient in proximal tubule has important implications for the mechanisms of near isosmotic volume reabsorption. A new fluorescence method was developed and applied to measure the transepithelial (sigma NaClTE) and basolateral membrane (sigma NaClcl) NaCl reflection coefficients in the isolated proximal straight tubule from rabbit kidney. For sigma NaClTE measurement, tubules were perfused with buffers containing 0 Cl, the Cl-sensitive fluorescent indicator 6-methoxy-N-[3-sulfopropyl] quinolinium and a Cl-insensitive indicator fluorescein sulfonate, and bathed in buffers of differing cryoscopic osmolalities containing NaCl. The transepithelial Cl gradient along the length of the tubule was measured in the steady state by a quantitative ratio imaging technique. A mathematical model based on the Kedem-Katchalsky equations was developed to calculate the axial profile of [Cl] from tubule geometry, lumen flow, water (Pf) and NaCl (PNaCl) permeabilities, and sigma NaClTE. A fit of experimental results to the model gave PNaCl = (2.25 +/- 0.2) x 10(-5) cm/s and sigma NaClTE = 0.98 +/- 0.03 at 23 degrees C. For measurement of sigma NaClbl, tubule cells were loaded with SPQ in the absence of Cl. NaCl solvent drag was measured from the time course of NaCl influx in response to rapid (less than 1 s) Cl addition to the bath solution. With bath-to-cell cryoscopic osmotic gradients of 0, -60, and +30 mosmol, initial Cl influx was 1.23, 1.10, and 1.25 mM/s; a fit to a mathematical model gave sigma NaClbl = 0.97 +/- 0.04. These results indicate absence of NaCl solvent drag in rabbit proximal tubule. The implications of these findings for water and NaCl movement in proximal tubule are evaluated