Direct probing of photoinduced electron transfer in a self- assembled biomimetic [2Fe2S]-hydrogenase complex using ultrafast vibrational spectroscopy

A pyridyl-functionalized diiron dithiolate complex, [μ-(4-pyCH2−NMI-S2)Fe2(CO)6] (3, py = pyridine(ligand), NMI = naphthalene monoimide) was synthesized and fully characterized. In the presence of zinc tetraphenylporphyrin (ZnTPP), a self-assembled 3·ZnTPP complex was readily formed in CH2Cl2 by the coordination of the pyridyl nitrogen to the porphyrin zinc center. Ultrafast photoinduced electron transfer from excited ZnTPP to complex 3 in the supramolecular assembly was observed in real time by monitoring the ν(CO) and ν(CO)NMI spectral changes with femtosecond time-resolved infrared (TRIR) spectroscopy. We have confirmed that photoinduced charge separation produced the monoreduced species by comparing the time-resolved IR spectra with the conventional IR spectra of 3•− generated by reversible electrochemical reduction. The lifetimes for the charge separation and charge recombination processes were found to be τCS = 40 ± 3 ps and τCR = 205 ± 14 ps, respectively. The charge recombination is much slower than that in an analogous covalent complex, demonstrating the potential of a supramolecular approach to extend the lifetime of the chargeseparated state in photocatalytic complexes. The observed vibrational frequency shifts provide a very sensitive probe of the delocalization of the electron-spin density over the different parts of the Fe2S2 complex. The TR and spectro-electrochemical IR spectra, electron paramagnetic resonance spectra, and density functional theory calculations all show that the spin density in 3•− is delocalized over the diiron core and the NMI bridge. This delocalization explains why the complex exhibits low catalytic dihydrogen production even though it features a very efficient photoinduced electron transfer. The ultrafast porphyrin-to-NMIS2−Fe2(CO)6 photoinduced electron transfer is the first reported example of a supramolecular Fe2S2-hydrogenase model studied by femtosecond TRIR spectroscopy. Our results show that TRIR spectroscopy is a powerful tool to investigate photoinduced electron transfer in potential dihydrogen-producing catalytic complexes, and that way to optimize their performance by rational approaches.

Electronic structure of Pd multi-layers on Re(0001): the role of charge transfer

Understanding the origin of the properties of metal-supported metal thin films is important for the rational design of bimetallic catalysts and other applications, but it is generally difficult to separate effects related to strain from those arising from interface interactions. Here we use density functional (DFT) theory to examine the structure and electronic behavior of few-layer palladium films on the rhenium (0001) surface, where there is negligible interfacial strain and therefore other effects can be isolated. Our DFT calculations predict stacking sequences and interlayer separations in excellent agreement with quantitative low-energy electron diffraction experiments. By theoretically simulating the Pd core-level X-ray photoemission spectra (XPS) of the films, we are able to interpret and assign the basic features of both low-resolution and high-resolution XPS measurements. The core levels at the interface shift to more negative energies, rigidly following the shifts in the same direction of the valence d-band center. We demonstrate that the valence band shift at the interface is caused by charge transfer from Re to Pd, which occurs mainly to valence states of hybridized s-p character rather than to the Pd d-band. Since the d-band filling is roughly constant, there is a correlation between the d-band center shift and its bandwidth. The resulting effect of this charge transfer on the valence d-band is thus analogous to the application of a lateral compressive strain on the adlayers. Our analysis suggests that charge transfer should be considered when describing the origin of core and valence band shifts in other metal / metal adlayer systems.

An experimental and theoretical investigation into positron and electron scattering from formaldehyde

We report on measurements of total cross sections (TCSs) for positron scattering from the fundamental organic molecule formaldehyde (CH(2)O). The energy range of these measurements was 0.26-50.3 eV, whereas the energy resolution was similar to 260 meV. To assist us in interpreting these data, Schwinger multichannel level calculations for positron elastic scattering from CH(2)O were also undertaken (0.5-50 eV). These calculations, incorporating an accurate model for the target polarization, are found to be in good qualitative agreement with our measured data. In addition, in order to compare the behaviour of positron and electron scattering from this species, independent atom model-screened additivity rule theoretical electron TCSs, now for energies in the range 1-10 000 eV, are also reported.

Dipole polarizability and Rayleigh light scattering by the hydrated electron

Assuming the existence of a confined state of the electron in bulk water the polarizability of the hydrated electron is analyzed. Statistically uncorrelated supermolecular structures composed of seven water molecules (first solvation shell) with an extra electron were extracted from classical Monte Carlo simulation and used in quantum mechanical second-order Moller-Plesset calculations. It is found that the bound excess electron contributes with 274 a.u. to the total dipole polarizability of 345 a.u. for (H(2)O)(7)(-). From the calculated polarizabilities the Rayleigh elastic light scattering properties are inferred and found to considerably enhance activity and light depolarization. (C) 2009 Elsevier B.V. All rights reserved.

Self-assembling of phenothiazine compounds investigated by small-angle X-ray scattering and electron paramagnetic resonance spectroscopy

Small-angle X-ray scattering (SAXS) and electron paramagnetic resonance (EPR) have been carried out to investigate the structure of the self-aggregates of two phenothiazine drugs, chlorpromazine (CPZ) and trifluoperazine (TFP), in aqueous solution. In the SAXS studies, drug solutions of 20 and 60 mM, at pH 4.0 and 7.0, were investigated and the best data fittings were achieved assuming several different particle form factors with a homogeneous electron density distribution in respect to the water environment. Because of the limitation of scattering intensity in the q range above 0.15 angstrom(-1), precise determination of the aggregate shape was not possible and all of the tested models for ellipsoids, cylinders, or parallelepipeds fitted the experimental data equally well. The SAXS data allows inferring, however, that CPZ molecules might self-assemble in a basis set of an orthorhombic cell, remaining as nanocrystallites in solution. Such nanocrystals are composed of a small number of unit cells (up to 10, in c-direction), with CPZ aggregation numbers of 60-80. EPR spectra of 5- and 16-doxyl stearic acids bound to the aggregates were analyzed through simulation, and the dynamic and magnetic parameters were obtained. The phenothiazine concentration in EPR experiments was in the range of 5-60 mM. Critical aggregation concentration of TFP is lower than that for CPZ, consistent with a higher hydrophobicity of TFP. At acidic pH 4.0 a significant residual motion of the nitroxide relative to the aggregate is observed, and the EPR spectra and corresponding parameters are similar to those reported for aqueous surfactant micelles. However, at pH 6.5 a significant motional restriction is observed, and the nitroxide rotational correlation times correlate very well with those estimated for the whole aggregated particle from SAXS data. This implies that the aggregate is densely packed at this pH and that the nitroxide is tightly bound to it producing a strongly immobilized EPR spectrum. Besides that, at pH 6.5 the differences in motional restriction observed between 5- and 16-DSA are small, which is different from that observed for aqueous surfactant micelles.

Ab Initio Calculations of Structural Evolution and Conductance of Benzene-1,4-dithiol on Gold Leads

By performing at) initio density functional theory (DFT) calculations and electronic transport simulations based on the OFT nonequilibrium Green`s functions method we investigate how the conformational changes of a benzene-1,4-dithiol molecule bonded to gold affect the molecular transport as the electrodes are separated from each other. In particular we consider the full evolution of the stretching process until the Junction breaking point and compare results obtained with a standard semilocal exchange and correlation functional to those computed with a self-interaction corrected method. We conclude that the inclusion of self-interaction corrections is fundamental for describing both the molecule conductance and its stability against conformational fluctuations.

The role of carbon impurities on the Si(001)-c(4 x 4) surface reconstruction: Theoretical calculations

In this work we employ the state-of-the-art pseudopotential method, within a generalized gradient approximation to the density functional theory, combined with a recently developed method for the calculation of HREELS spectra to study a series of different proposed models for carbon incorporation on the silicon (001) surface. A fully discussion on the geometry, energetics and specially the comparison between experimental and theoretical STM images and electron energy loss spectra indicate that the Si(100)-c(4 x 4) is probably induced by Si-C surface dinners, in agreement with recent experimental findings. (C) 2009 Elsevier B.V. All rights reserved.

Coherent states of non-relativistic electron in the magnetic-solenoid field

In the present work we construct coherent states in the magnetic-solenoid field, which is a superposition of the Aharonov-Bohm field and a collinear uniform magnetic field. In the problem under consideration there are two kinds of coherent states, those which correspond to classical trajectories which embrace the solenoid and those which do not. The constructed coherent states reproduce exactly classical trajectories, maintain their form under the time evolution and form a complete set of functions, which can be useful in semiclassical calculations. In the absence of the solenoid field these states are reduced to the well known in the case of uniform magnetic field Malkin-Man`ko coherent states.

A dedicated setup for the measurement of the electron transport parameters in gases at large electric fields

Electron transport parameters are important in several areas ranging from particle detectors to plasma-assisted processing reactors. Nevertheless, especially at high fields strengths and for complex gases, relatively few data are published. A dedicated setup has been developed to measure the electron drift velocity and the first Townsend coefficient in parallel plate geometry. An RPC-like cell has been adopted to reach high field strengths without the risk of destructive sparks. The validation data obtained with pure Nitrogen will be presented and compared to a selection of the available literature and to calculations performed with Magboltz 2 version 8.6. The new data collected in pure Isobutane will then be discussed. This is the first time the electron drift velocity in pure Isobutane is measured well into the saturation region. Good agreement is found with expectations from Magboltz. (C) 2009 Elsevier B.V. All rights reserved.

Joint Experimental and Theoretical Analysis of Order Disorder Effects in Cubic BaZrO(3) Assembled Nanoparticles under Decaoctahedral Shape

Periodic first-principles calculations based on density functional theory at the B3LYP level has been carried out to investigate the photoluminescence (PL) emission of BaZrO(3) assembled nanoparticles at room temperature. The defect created in the nanocrystals and their resultant electronic features lead to a diversification of electronic recombination within the BaZrO(3) band gap. Its optical phenomena are discussed in the light of photoluminescence emission at the green-yellow region around 570 nm. The theoretical model for displaced atoms and/or angular changes leads to the breaking of the local symmetry, which is based on the refined structure provided by Rietveld methodology. For each situation a band structure, charge mapping, and density of states were built and analyzed. X-ray diffraction (XRD) patterns, UV-vis measurements, and field emission scanning electron microscopy (FE-SEM) images are essential for a full evaluation of the crystal structure and morphology.

Tightened Lieb-Oxford Bound for Systems of Fixed Particle Number

The Lieb-Oxford bound is a constraint upon approximate exchange-correlation functionals. We explore a nonempirical tightening of that bound in both universal and electron number-dependent form. The test functional is PBE. Regarding both atomization energies (slightly worsened) and bond lengths (slightly improved), we find the PBE functional to be remarkably insensitive to the value of the Lieb-Oxford bound. This both rationalizes the use of the original Lieb-Oxford constant in PBE and suggests that enhancement factors more sensitive to sharpened constraints await discovery.

Empirical analysis of the Lieb-Oxford bound in ions and molecules

Universal properties of the Coulomb interaction energy apply to all many-electron systems. Bounds on the exchange-correlation energy, in particular, are important for the construction of improved density functionals. Here we investigate one such universal property-the Lieb-Oxford lower bound-for ionic and molecular systems. In recent work [J Chem Phys 127, 054106 (2007)], we observed that for atoms and electron liquids this bound may be substantially tightened. Calculations for a few ions and molecules suggested the same tendency, but were not conclusive due to the small number of systems considered. Here we extend that analysis to many different families of ions and molecules, and find that for these, too, the bound can be empirically tightened by a similar margin as for atoms and electron liquids. Tightening the Lieb-Oxford bound will have consequences for the performance of various approximate exchange-correlation functionals. (C) 2008 Wiley Periodicals Inc.

Reaction microtextures of monazite: Correlation between chemical and age domains in the Nazare Paulista migmatite, SE Brazil

Back-scattered imaging, X-ray element mapping and electron microprobe analyzer (EMPA) chemical dating reveal complex compositional and age zoning in monazite crystals from different layers and textural positions in a garnet-bearing migmatite in SE Brazil. Y-rich (variable Y(2)O(3), averaging 2.5 wt.%) relict cores are preserved in mesosome and melanosome monazite, and correspond to 793 +/- 6 Ma inherited crystals possibly generated in a previous metamorphic event. These cores are overgrown and widely replaced by two generations of monazite, which are present in all migmatite layers. The first, also Y-rich (average 2.5 wt.% Y(2)O(3)), was produced at similar to 635 Ma during prograde metamorphism under subsolidus conditions, while the second has an Y-poor (<1.5 wt.% Y(2)O(3)), low Th/U signature, and precipitated from low Y and HREE anatectic melts produced by reactions in which garnet was inert. Quartz-rich trondhjemitic leucosome represents lower temperature melt (bearing some subsolidus quartz and garnet with included monazite) formed at temperatures below muscovite breakdown; its Y-poor monazite indicates an age of 617 +/- 6 Ma. Granitic leucosomes formed close to peak metamorphic conditions (T>750 degrees C) above muscovite breakdown have their slightly younger character confirmed by a 609 +/- 7 Ma low-Y monazite age. A similar 606 +/- 5 Ma age was obtained for low-Y monazite rims and domains in mesosome and melanosome, and reflects the time of monazite saturation in interstitial granitic melt that was trapped in these layers. Our results confirm that inherited monazite crystals can be preserved during partial melting at temperatures above muscovite breakdown. Moreover, careful textural control aided by X-ray chemical mapping may allow monazite generated at different stages in a similar to 25 Myr prograde metamorphic path to be identified and dated using an electron microprobe. (C) 2008 Elsevier B.V. All rights reserved.

Experimental Evidence of the Occurrence of Intramolecular Electron Transfer in Catalyzed 1,2-Dioxetane Decomposition

The activation parameters for the thermal decomposition of 13 acridinium-substituted 1,2-dioxetanes, bearing an aromatic moiety, were determined and their chemiluminescence emission quantum yields estimated, utilizing in situ photosensitized 1,2-dioxetane generation and observation of its thermal decomposition kinetics, without isolation of these highly unstable cyclic peroxides. Decomposition rate constants show linear free-energy correlation for electron-withdrawing substituents, with a Hammett reaction constant of rho = 1.3 +/- 0.1, indicating the occurrence of an intramolecular electron transfer from the acridinium moiety to the 1,2-dioxetane ring, as postulated by the intramolecular chemically initiated electron exchange luminescence (CIEEL) mechanism. Emission quantum yield behavior can also be rationalized on the basis of the intramolecular CIEEL mechanism, additionally evidencing its occurrence in this transformation. Both relations constitute the first experimental evidence for the occurrence of the postulated intramolecular electron transfer in the catalyzed and induced decomposition of properly substituted 1,2-dioxetanes.

Synthesis, spectroscopic characterization and X-ray structures of five-coordinate diorganotin(IV) complexes containing 5-hydroxypyrazoline derivatives as ligands

Four new diorganotin(IV) complexes have been prepared from R(2)SnCl(2) (R = Me, Ph) with the ligands 5-hydroxy-3-metyl-5-phenyl-1-(S-benzildithiocarbazate)-pyrazoline (H(2)L(1)) and 5-hydroxy-3-methyl-5-phenyl-1-(2-thiophenecarboxylic)-pyrazoline (H(2)L(2)). The complexes were characterized by elemental analysis, IR. (1)H (13)C, (119)Sn NMR and Mossbauer spectroscopes The complexes [Me(2)SnL(1)], [Ph(2)SnL(1)] and [Me(2)SnL(2)] were also studied by single crystal X-ray diffraction and the results showed that the Sn(IV) central atom of the complexes adopts a distorted trigonal bipyramidal (TBP) geometry with the N atom of the ONX-tridentate (X = O and S) ligand and two organic groups occupying equatorial sites. The C-Sn-C angles for [Me(2)Sn(L(1))] and [Ph(2)Sn(L(1))] were calculated using a correlation between (119)Sn Mossbauer and X-ray crystallographic data based on the point-charge model Theoretical calculations were performed with the B3LYP density functional employing 3-21G(*) and DZVP all electron basis sets showing good agreement with experimental findings General and Sn(IV) specific IR harmonic frequency scale factors for both basis sets were obtained from comparison with selected experimental frequencies (C) 2010 Elsevier B V All rights reserved