Reactivity of diatomics and of ethylene on zeolite-supported 13-atom platinum nanoclusters

Monodisperse Pt clusters of 132 atoms, supported on the zeolites NaY and KL and saturated with chemisorbed hydrogen, are investigated as well-defined model catalysts for reactions of CO, NO, O2 and ethene. CO reacts within <10 min, leading to the formation of dinuclear Pt carbonyl molecular clusters. The similar behaviour of NO suggests an analogous reaction. In stark contrast, O2 reveals very sluggish reaction on a timescale of days although the reaction with chemisorbed hydrogen to H2O is thermodynamically still favoured. This is ascribed to the inability of O2 to adsorb atop of Pt when all neighbouring sites are blocked by chemisorbed hydrogen. The hydrogenation reaction of ethene yields ethane as the only product. The turnover frequency at room temperature is somewhat lower than the one reported for the same reaction on Pt(111) single crystal surfaces or on Pt nanoparticles, but its activation energy is double of that typically found in the other systems. This means that the reaction which has been known to be structure-insensitive becomes structure-sensitive for catalyst clusters as small as 13 atoms. This fact is ascribed to a significantly larger binding energy of H on Pt as a consequence of the small cluster size and the influence of the support.http://pubs.rsc.org/en/Journals/JournalIssues/CY#!recentarticles&advhb2016Chemistr

State-resolved valence shell photoionization of Be-like ions: experiment and theory

High-resolution photoionization experiments were carried out using beams of Be-like C$^{2+}$, N$^{3+}$, and O$^{4+}$ ions with roughly equal populations of the $^1$S ground-state and the $^3$P$^o$ manifold of metastable components. The energy scales of the experiments are calibrated with uncertainties of 1 to 10 meV depending on photon energy. Resolving powers beyond 20,000 were reached allowing for the separation of contributions from the individual metastable $^3$P$^o_0$, $^3$P$^o_1$, and $^3$P$^o_2$ states. The measured data compare favourably with semi-relativistic Breit-Pauli R-matrixComment: 23 figures and 3 table

Hyperspherical partial wave calculation for double photoionization of the helium atom at 20 eV excess energy

Hyperspherical partial wave approach has been applied here in the study of double photoionization of the helium atom for equal energy sharing geometry at 20 eV excess energy. Calculations have been done both in length and velocity gauges and are found to agree with each other, with the CCC results and with experiments and exhibit some advantages of the corresponding three particle wave function over other wave functions in use.Comment: 11 pages, 1 figure, submitted to J. Phys B: At. Mol. Opt. Phys; v2 - revised considerably, rewritten using ioplatex clas

Differential energy measurement between He- and Li-like uranium intra-shell transitions

We present the first clear identification and highly accurate measurement of the intra-shell transition 1s2p\, ^3P_2 \to 1s2s\, ^3S_1 of He-like uranium performed via X-ray spectroscopy. The present experiment has been conducted at the gas-jet target of the ESR storage ring in GSI (Darmstadt, Germany) where a Bragg spectrometer, with a bent germanium crystal, and a Ge(i) detector were mounted. Using the ESR deceleration capabilities, we performed a differential measurement between the 1s2p\, ^3P_2 \to 1s2s\, ^3S_1 He-like U transition energy, at 4510 eV, and the 1s^22p\ ^2P_{3/2} \to 1s^22s\, ^2S_{1/2} Li-like U transition energy, at 4460 eV. By a proper choice of the ion velocities, the X-ray energies from the He- and Li-like ions could be measured, in the laboratory frame, at the same photon energy. This allowed for a drastic reduction of the experimental systematic uncertainties, principally due to the Doppler effect, and for a comparison with the theory without the uncertainties arising from one-photon QED predictions and nuclear size corrections

Beam Instrumentation for CRYRING@@ESR

BACKGROUND: The disulfide-bonded region (DSR) of HIV-1 gp41 mediates association with gp120 and plays a role in transmission of receptor-induced conformational changes in gp120 to gp41 that activate membrane fusion function. In this study, forced viral evolution of a DSR mutant that sheds gp120 was employed to identify domains within gp120-gp41 that are functionally linked to the glycoprotein association site. RESULTS: The HIV-1AD8 mutant, W596L/K601D, was serially passaged in U87.CD4.CCR5 cells until replication was restored. Whereas the W596L mutation persisted throughout the cultures, a D601H pseudoreversion in the DSR partially restored cell-free virus infectivity and virion gp120-gp41 association, with further improvements to cell-free virus infectivity following a 2nd-site D674E mutation in the membrane-proximal external region (MPER) of gp41. In an independent culture, D601H appeared with a deletion in V4 (Thr-394-Trp-395) and a D674N substitution in the MPER, however this MPER mutation was inhibitory to W596L/K601H cell-free virus infectivity. While cell-free virus infectivity was not fully restored for the revertant genotypes, their cell-to-cell transmission approached the levels observed for WT. Interestingly, the functional boost associated with the addition of D674E to W596L/K601H was not observed for cell-cell fusion where the cell-surface expressed glycoproteins function independently of virion assembly. The W596L/K601H and W596L/K601H/D674E viruses exhibited greater sensitivity to neutralization by the broadly reactive MPER directed monoclonal antibodies, 2F5 and 4E10, indicating that the reverting mutations increase the availability of conserved neutralization epitopes in the MPER. CONCLUSIONS: The data indicate for the first time that functional crosstalk between the DSR and MPER operates in the context of assembled virions, with the Leu-596-His-601-Glu-674 combination optimizing viral spread via the cell-to-cell route. Our data also indicate that changes in the gp120-gp41 association site may increase the exposure of conserved MPER neutralization epitopes in virus