Renner-Teller and Fermi resonance interactions for the v3=1 and v7=2 vibronic levels in the A2Πu and X2Πg electronic states of HC4H+

The excitation of the v(3) = 1 (σ(g)(+) C-C stretch) and the v(7) = 2 (π(g)(2) C≡C-C bend) modes in the A(2)Π(u) electronic state of diacetylene cations results in Renner-Teller (R-T) and Fermi interactions. The 3(0)(1) and 7(0)(2) vibronic bands in the A(2)Π(u)-X(2)Π(g) transition of HC(4)H(+) have been measured with rotational resolution using cavity ringdown spectroscopy in a supersonic slit jet discharge. The analysis yields T(00) = 20520.828(4) cm(-1), B' = 0.14047(2) cm(-1), and A' = -17.95(1) cm(-1) for the v(3) = 1 and T(00) = 20573.659(4) cm(-1), B' = 0.14018(3) cm(-1), and A' = -11.55(1) cm(-1) for the v(7) = 2 level in the A(2)Π(u) electronic state. A vibronic analysis has been carried out taking into consideration the R-T, spin-orbit, and Fermi resonance interactions between the ν(3) and ν(7) modes. The levels are fitted to the eigenvalues of an appropriate Hamiltonian matrix. This yields the vibrational frequencies ω(3)′ = 811.8 cm(-1) and ω(7)′ = 403.2 cm(-1), Renner parameter ε(7)′ = 0.065, Fermi coefficients W(1)′ = 10.3 cm(-1) and W(2)′ = 5.1 cm(-1), and spin-orbit interaction constant A(SO)′ = -31.1 cm(-1). A corresponding R-T analysis has been carried out for the X(2)Π(g) ground state of HC(4)H(+) using data available in the literature [Callomon, J. H. Can. J. Phys. 1956, 34, 1046]. This gives ω(3)" = 956.2 cm(-1), ω(7)" = 435.4 cm(-1), ε(7)" = 0.028, W(1)" = 7.2 cm(-1), W(2)" = 10.9 cm(-1), and A(SO)" = -33.3 cm(-1).     

Direct observation of lithium staging in partially delithiated LiFePO4 at atomic resolution

Lithium ions in LiFePO(4) were observed directly at atomic resolution by an aberration-corrected annular-bright-field scanning transmission electron microscopy technique. In addition, it was found in partially delithiated LiFePO(4) that the remaining lithium ions preferably occupy every second layer, along the b axis, analogously to the staging phenomenon observed in some layered intercalation compounds. This new finding challenges previously proposed LiFePO(4)/FePO(4) two-phase separation mechanisms.     

Conformational studies of the robust 2-Cys peroxiredoxin Salmonella typhimurium AhpC by solution phase hydrogen/deuterium (H/D) exchange monitored by electrospray ionization mass spectrometry

This is the first comprehensive HX-MS study of a "robust" 2-Cys peroxiredoxin (Prx), namely Salmonella typhimurium AhpC (StAhpC). Prx proteins control intracellular peroxide levels and are abundant antioxidant proteins in eukaryotes, archaea and bacteria. Crystal structural analyses and structure/activity studies of several bacterial and mammalian 2-Cys Prxs have revealed that the activity of 2-Cys Prxs is regulated by redox-dependent oligmerization and a sensitivity of the active site cysteine residue to overoxidation. The propensity to overoxidation is linked to the conformational flexibility of the peroxidatic active site loop. The HX-MS results emphasize the modulation of the conformational motility of the active site loop by disulfide formation. To obtain information on the conformational impact of decamer formation on the active site loop motility, mutants with Thr77 substituted by Ile, a decamer-disrupting mutation or by Val, a decamer-stabilizing mutation, were studied. For the isoleucine mutant, enhanced mobility was observed for regions encompassing the α4 helix located in the dimer-dimer interface and regions surrounding the peroxidatic loop. In contrast, the T77V mutation resulted in an increase in conformational stability in most regions of the protein except for the active site loop and the region encompassing the resolving cysteine.     

Mixed conductivity in nanocrystalline highly acceptor doped cerium oxide thin films under oxidizing conditions

We report on the investigation of 10 mol% gadolinium-doped cerium oxide thin films of various microstructures prepared by pulsed laser deposition. Depending on substrate, growth conditions and hence microstructure, the electric conductivity values vary considerably by several orders of magnitude. Remarkably, in the sample with the highest grain boundary density, we even have evidence of substantial electronic conductance under oxidizing conditions despite the large acceptor level. This possibly surprising result can be explained by an increased space charge potential at the grain boundaries in combination with the small grain size of 10 nm that leads to an enrichment of excess electrons while the ion conduction is simultaneously blocked by vacancy-depleted regions.     

MAFF — The Munich accelerator for fission fragments

At the new high flux reactor FRM-II in Munich the accelerator MAFF (Munich accelerator for fission fragments) is under design. In the high neutron flux of 10¹⁴ n/cm² s up to 10¹⁴ neutron-rich fission fragments per second are produced in the 1 g U-235 target. Ions with an energy of 30 keV are extracted from the ion source. In the mass separator two isotopes can be selected. One of the beams is used for low energy experiments, the other one is injected into an ECRIS (or EBIS) for charge breeding to a q/A≥0.16. A gas filled RFQ cooler is used for emittance improvement. The subsequent LINAC delivers beams with an energy ranging from 3.7 MeV/u to 5.9 MeV/u. New IH structures are being developed at the Munich tandem laboratory. A small storage ring is planned in a further stage to recycle the fission fragments. A thin target foil can be placed into this ring, e.g., for synthesis of super-heavy elements. The through-going beam tube has been installed in the heavy water tank of the reactor. Tests of the target ion source in a special oven to test long term stability and safety tests were in progress.     

Synthesis of photosensitizer pairs containing Ru(bpy)3 2+ and an electron acceptor (viologen) linked by a hydrocarbon chain

Conclusions Two Ru(bpy)₃ ²⁺-viologen complexes, in which the components are linked by a hydrocarbon chain, were synthesized and characterized by PMR, visible, and UV spectrophotometry.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 700–703, March, 1989.