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211.
Paramagnetic bridging hydrides of relevance to catalytic hydrogen evolution at metallosulfur centers
Jablonskytė A Wright JA Fairhurst SA Peck JN Ibrahim SK Oganesyan VS Pickett CJ 《Journal of the American Chemical Society》2011,133(46):18606-18609
Paramagnetic hydrides are likely intermediates in hydrogen-evolving enzymic and molecular systems. Herein we report the first spectroscopic characterization of well-defined paramagnetic bridging hydrides. Time-resolved FTIR spectroelectrochemical experiments on a subsecond time scale revealed that single-electron transfer to the μ-hydride di-iron dithiolate complex 1 generates a 37-electron valence-delocalized species with no gross structural reorganization of the coordination sphere. DFT calculations support and (1)H and (2)H EPR measurements confirmed the formation an S = ? paramagnetic complex (g = 2.0066) in which the unpaired spin density is essentially symmetrically distributed over the two iron atoms with strong hyperfine coupling to the bridging hydride (A(iso) = -75.8 MHz). 相似文献
212.
Kania R Frederix PW Wright JA Ulijn RV Pickett CJ Hunt NT 《The Journal of chemical physics》2012,136(4):044521
The solution-phase photochemistry of the [FeFe] hydrogenase subsite model (μ-S(CH(2))(3)S)Fe(2)(CO)(4)(PMe(3))(2) has been studied using ultrafast time-resolved infrared spectroscopy supported by density functional theory calculations. In three different solvents, n-heptane, methanol, and acetonitrile, relaxation of the tricarbonyl intermediate formed by UV photolysis of a carbonyl ligand leads to geminate recombination with a bias towards a thermodynamically less stable isomeric form, suggesting that facile interconversion of the ligand groups at the Fe center is possible in the unsaturated species. In a polar or hydrogen bonding solvent, this process competes with solvent substitution leading to the formation of stable solvent adduct species. The data provide further insight into the effect of incorporating non-carbonyl ligands on the dynamics and photochemistry of hydrogenase-derived biomimetic compounds. 相似文献
213.
LR Webster SK Ibrahim JA Wright CJ Pickett 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(37):11798-11803
We show that a robust molybdenum hydride system can sustain photoelectrocatalysis of a hydrogen evolution reaction at boron-doped, hydrogen-terminated, p-type silicon. The photovoltage for the system is about 600-650?mV and the current densities, which can be sustained at the photocathode in non-catalytic and catalytic regimes, are similar to those at a photoinert vitreous carbon electrode. The kinetics of electrocatalysed hydrogen evolution at the photocathode are also very similar to those measured at vitreous carbon-evidently visible light does not significantly perturb the catalytic mechanism. Importantly, we show that the doped (1-10?Ω?cm) p-type Si can function perfectly well in the dark as an ohmic conductor and this has allowed direct comparison of the cyclic voltammetric behaviour of the response of the system under dark and illuminated conditions at the same electrode. The p-type Si we have employed optimally harvests light energy in the 600-700?nm region and with 37?mW?cm(-2) illumination in this range; the light to electrochemical energy conversion is estimated to be 2.8?%. The current yield of hydrogen under broad tungsten halide lamp illumination at 90?mW?cm(-2) is (91±5)?% with a corresponding chemical yield of (98±5)?%. 相似文献
214.
Maddox BR Lazicki A Yoo CS Iota V Chen M McMahan AK Hu MY Chow P Scalettar RT Pickett WE 《Physical review letters》2006,96(21):215701
We present resonant inelastic x-ray scattering and x-ray emission spectroscopy results on Gd metal to 113 GPa which suggest Kondo-like aspects in the delocalization of 4f electrons. Analysis of the resonant inelastic x-ray scattering data reveals a prolonged and continuous delocalization with volume throughout the entire pressure range, so that the volume-collapse transition at 59 GPa is only part of the phenomenon. Moreover, the Lgamma1 x-ray emission spectroscopy spectra indicate no apparent change in the bare 4f moment across the collapse, suggesting that Kondo screening is responsible for the expected Pauli-like behavior in magnetic susceptibility. 相似文献
215.
Ab initio band theory including correlations due to intra-atomic repulsion is applied to study charge disproportionation and charge and spin ordering in insulating Na0.5CoO2. Various ordering patterns (zigzag and two striped) for four-Co supercells are analyzed before focusing on the observed "out-of-phase stripe" pattern of antiferromagnetic Co4+ spins along charge-ordered stripes. This pattern relieves frustration and shows distinct analogies with the cuprate layers: a bipartite lattice of antialigned spins, with axes at 90degrees angles. Substantial distinctions with cuprates are also discussed, including the tiny gap of a new variant of "charge-transfer" type within the Co 3d system. 相似文献
216.
F Ronning JX Zhu T Das MJ Graf RC Albers HB Rhee WE Pickett 《J Phys Condens Matter》2012,24(29):294206
Density functional theory calculations of the electronic structure of Ce- and Pu-based heavy fermion superconductors in the so-called 115 family are performed. The gap equation is used to consider which superconducting order parameters are most favorable assuming a pairing interaction that is peaked at (π, π, qz)—the wavevector for the antiferromagnetic ordering found in close proximity. In addition to the commonly accepted dx2?y2 order parameter, there is evidence that an extended s-wave order parameter with nodes is also plausible. We discuss whether these results are consistent with current observations and possible measurements that could help distinguish between these scenarios. 相似文献
217.