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PubMed2004

Electron delocalization and electrostatic repulsion at the origin of the strong spin coupling in mixed-valence keggin polyoxometalates: ab initio calculations of the one- and two-electron processes.

We present here a general theoretical procedure to treat the problem of electron delocalization and magnetic interactions in high-nuclearity mixed valence clusters based on polyoxometalates. The main interactions between the delocalized electrons of mixed-valence polyoxometalate anions are extracted from valence spectroscopy ab initio calculations on embedded fragments. Electron transfer, magnetic coupling and exchange transfer parameters between nearest and next-nearest-neighbor metal ions, as well as the value of the electrostatic repulsion between pairs of metal ions are determined. These parameters are introduced in a model Hamiltonian that considers the whole anion. It thus provides macroscopic properties that should be compared with the experimental data. This method is applied to a two-electron-reduced polyoxowolframate Keggin anion. The results demonstrate that the electron transfer processes, combined with the Coulombic repulsion between the "extra" electrons, induce a strong antiferromagnetic coupling between the two delocalized spins providing a definite explanation of the diamagnetic properties of these high nuclearity mixed-valence clusters.

Journal Article↗
PubMed2005

Probing molecular wires: synthesis, structural, and electronic study of donor-acceptor assemblies exhibiting long-range electron transfer.

A series of donor-acceptor arrays (C60-oligo-PPV-exTTF; 16-20) incorporating pi-conjugated oligo(phenylenevinylene) wires (oligo-PPV) of different length between pi-extended tetrathiafulvalene (exTTF) as electron donor and C60 as electron acceptor has been prepared by multistep convergent synthetic approaches. The electronic interactions between the three electroactive species present in 16-20 were investigated by UV-visible spectroscopy and cyclic voltammetry (CV). Our studies clearly show that, although the C60 units are connected to the exTTF donors through a pi-conjugated oligo-PPV framework, no significant electronic interactions are observed in the ground state. Interestingly, photoinduced electron-transfer processes over distances of up to 50 Angstroms afford highly stabilized radical ion pairs. The measured lifetimes for the photogenerated charge-separated states are in the range of hundreds of nanoseconds (approximately 500 ns) in benzonitrile, regardless of the oligomer length (i.e., from the monomer to the pentamer). A different lifetime (4.35 micros) is observed for the heptamer-containing array. This difference in lifetime has been accounted for by the loss of planarity of the oPPV moiety that increases with the wire length, as established by semi-empirical (PM3) theoretical calculations carried out with 19 and 20. The charge recombination dynamics reveal a very low attenuation factor (beta = 0.01 +/- 0.005 Angstroms(-1)). This beta value, as well as the strong electron coupling (V approximately 5.5 cm(-1)) between the donor and the acceptor units, clearly reveals a nanowire behavior for the pi-conjugated oligomer, which paves the way for applications in nanotechnology.

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PubMed2006

Electron group functions for the analysis of the electronic structures of molecules.

The electronic structure of a vast majority of molecular systems can be understood in terms of electron groups and their wave functions. They serve as a natural basis for bringing intuitive chemical and physical concepts into quantum chemical calculations. This article considers the general electron group functions formalism as well as its simple geminal version. We try to characterize the wave function with the group structure and its capabilities in actual calculations. For this purpose we implement a variational method based on the wave function in the form of an antisymmetrized product of strongly orthogonal group functions and perform a series of electronic structure calculations for small molecules and model systems. The most important point studied is the relation between the choice of electron groups and the results obtained. We consider energetic characteristics as well as optimal geometry parameters. In view of practical importance, the structure of variationally optimized local one-electron states is considered in detail as well as intuitive characteristics of chemical bonds.

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PubMed2000

Direct measurement of electron beam scattering in the environmental scanning electron microscope using phosphor imaging plates

Phosphor imaging plate technology has made it possible to directly image the distribution of primary beam electrons and scattered electrons in the environmental scanning electron microscope. The phosphor plate is exposed under electron scattering conditions in the microscope chamber. When processed, the electron intensity distribution is displayed as a digital image. The image is a visual representation of the electron probe and skirt and may provide the basis for a more accurate model.

Journal Article↗
PubMed2000

Charge contrast imaging of material growth and defects in environmental scanning electron miscroscopy--linking electron emission and cathodoluminescence

An electron-based technique for the imaging of crystal defect distribution such as material growth histories in non- and poorly conductive materials has been identified in the variable pressure or environmental scanning electron microscope. Variations in lattice coherence at the meso-scale can be imaged in suitable materials. Termed charge contrast imaging (CCI), the technique provides images that correlate exactly with emitted light or cathodoluminescence in suitable materials. This correlation links cathodoluminescence and an electron emission. The specific operating conditions for observation of these images reflect a complex interaction between the electron beam, the positive ions generated by electron-gas interactions in the chamber, a biased detector, and the sample. The net result appears to be the suppression of all but very near surface electron emission from the sample, probably from of the order of a few nanometres. Consequently, CCI are also sensitive to very low levels of surface contaminants. Successful imaging of internal structures in a diverse range of materials indicate that the technique will become an important research tool.

Journal Article↗
PubMedDate not supplied

High-temperature electron backscatter diffraction and scanning electron microscopy imaging techniques: in-situ investigations of dynamic processes.

In-situ heating experiments have been conducted at temperatures of approximately 1200 K utilising a new design of scanning electron microscope, the CamScan X500. The X500 has been designed to optimise the potential for electron backscatter diffraction (EBSD) analysis with concomitant in-situ heating experimentation. Features of the new design include an inclined field emission gun (FEG) column, which affords the EBSD geometrical requirement of a high (typically 160 degrees) angle between the incoming electron beam and specimen surface, but avoids complications in heating-stage design and operation by maintaining it in a horizontal orientation. Our studies have found that secondary electron and orientation contrast imaging has been possible for a variety of specimen materials up to a temperature of at least 900 degrees C, without significant degradation of imaging quality. Electron backscatter diffraction patterns have been acquired at temperatures of at least 900 degrees C and are of sufficient quality to allow automated data collection. Automated EBSD maps have been produced at temperatures between 200 degrees C and 700 degrees C in aluminium, brass, nickel, steel, quartz, and calcite, and even at temperatures >890 degrees C in pure titanium. The combination of scanning electron microscope imaging techniques and EBSD analysis with high-temperature in-situ experiments is a powerful tool for the observation of dynamic crystallographic and microstructural processes in metals, semiconductor materials, and ceramics.

Journal Article↗
PubMed2000

Contrast of Highly Dispersed Metal Nanoparticles in High-resolution Secondary Electron and Backscattered Electron Images of Supported Metal Catalysts.

Platinum nanoparticles finely dispersed in activated carbon powders have been observed with high contrast in secondary electron (SE) and backscattered electron (BE) images. The factors that contribute to the visibility of small metal particles in high-resolution BE and SE images are discussed. Monte Carlo simulations provided insight into the scattering of electrons by small, heavy-element particles located on, or embedded in, light-element supports. The visibility of Pt nanoparticles in BE images depends on many factors including the size and the location of the Pt particles, the energy of the incident electrons, and the size of the electron probe. The SE signals generated by backscattered electrons may not significantly contribute to the visibility of small Pt particles in high-resolution SE images of carbon supported Pt catalysts. Only those small Pt particles that are located on or very close to the surface of the carbon support can be revealed in high-resolution SE images.

Journal Article↗
PubMed2002

Regulation of proton-to-electron stoichiometry in photosynthetic electron transport: physiological function in photoprotection.

The primary stable products of photosynthetic electron flow are NADPH and ATP. Stoichiometry of their production depends on the ratio of protons pumped across the thylakoid membrane to electrons passed through the electron transport pathway (H(+)/e(-) ratio). Flexible requirements of the ATP/NADPH ratio by various assimilatory reactions in chloroplasts must be fulfilled by the H(+)/e(-) ratio during the electron flow. In addition to the well-known role of Delta pH during ATP synthesis, Delta pH also functions as a trigger of the down-regulation of photosystem II (PSII) photochemistry. Excessive light energy is safely dissipated as heat by this regulatory process to suppress the generation of toxic reactive oxygen species. Thus, regulation of the H(+)/e(-) ratio may function in the photoprotection, as well as in the regulation of the ATP/NADPH production ratio. It has long been the consensus that the H(+)/e(-) ratio can be controlled by regulating the proton-transporting Q-cycle in the cytochrome b(6)f complex and by the cyclic electron flow around photosystem I (PSI). Despite the possible physiological importance and the long history of interest, the molecular identity of Q-cycle regulation and the cyclic electron flow around PSI have been remained unclear. The recent improvements in research tools, including the genetic approach using chlorophyll fluorescence imaging and establishment of the chloroplast transformation technique, are providing new insights into classical topics. In this review, we focus on regulation of the H(+)/e(-) ratio especially from the view of photosynthetic regulation.

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PubMed2005

The interaction domain of the redox protein adrenodoxin is mandatory for binding of the electron acceptor CYP11A1, but is not required for binding of the electron donor adrenodoxin reductase.

Adrenodoxin (Adx) is a [2Fe-2S] ferredoxin involved in electron transfer reactions in the steroid hormone biosynthesis of mammals. In this study, we deleted the sequence coding for the complete interaction domain in the Adx cDNA. The expressed recombinant protein consists of the amino acids 1-60, followed by the residues 89-128, and represents only the core domain of Adx (Adx-cd) but still incorporates the [2Fe-2S] cluster. Adx-cd accepts electrons from its natural redox partner, adrenodoxin reductase (AdR), and forms an individual complex with this NADPH-dependent flavoprotein. In contrast, formation of a complex with the natural electron acceptor, CYP11A1, as well as electron transfer to this steroid hydroxylase is prevented. By an electrostatic and van der Waals energy minimization procedure, complexes between AdR and Adx-cd have been proposed which have binding areas different from the native complex. Electron transport remains possible, despite longer electron transfer pathways.

Adrenodoxin↗
PubMed2001

Calculation of the electronic structure of carbon films using electron energy loss spectroscopy.

The detailed understanding of the electronic properties of carbon-based materials requires the determination of their electronic structure and more precisely the calculation of their joint density of states (JDOS) and dielectric constant. Low electron energy loss spectroscopy (EELS) provides a continuous spectrum which represents all the excitations of the electrons within the material with energies ranging between zero and about 100 eV. Therefore, EELS is potentially more powerful than conventional optical spectroscopy which has an intrinsic upper information limit of about 6 eV due to absorption of light from the optical components of the system or the ambient. However, when analysing EELS data, the extraction of the single scattered data needed for Kramers Kronig calculations is subject to the deconvolution of the zero loss peak from the raw data. This procedure is particularly critical when attempting to study the near-bandgap region of materials with a bandgap below 1.5 eV. In this paper, we have calculated the electronic properties of three widely studied carbon materials; namely amorphous carbon (a-C), tetrahedral amorphous carbon (ta-C) and C60 fullerite crystal. The JDOS curve starts from zero for energy values below the bandgap and then starts to rise with a rate depending on whether the material has a direct or an indirect bandgap. Extrapolating a fit to the data immediately above the bandgap in the stronger energy loss region was used to get an accurate value for the bandgap energy and to determine whether the bandgap is direct or indirect in character. Particular problems relating to the extraction of the single scattered data for these materials are also addressed. The ta-C and C60 fullerite materials are found to be direct bandgap-like semiconductors having a bandgaps of 2.63 and 1.59eV, respectively. On the other hand, the electronic structure of a-C was unobtainable because it had such a small bandgap that most of the information is contained in the first 1.2 eV of the spectrum, which is a region removed during the zero loss deconvolution.

Journal Article↗
PubMed2002

Electronic spectra and structures of d2 molybdenum-oxo complexes. Effects of structural distortions on orbital energies, two-electron terms, and the mixing of singlet and triplet states.

Molybdenum-oxo ions of the type [Mo(IV)OL(4)Cl](+) (L = CNBu(t), PMe(3), (1)/(2)Me(2)PCH(2)CH(2)PMe(2)) have been studied by X-ray crystallography, vibrational spectroscopy, and polarized single-crystal electronic absorption spectroscopy (300 and ca. 20 K) in order to investigate the effects of the ancillary ligand geometry on the properties of the MotriplebondO bond. The idealized point symmetries of the [Mo(IV)OL(4)Cl](+) ions were established by X-ray crystallographic studies of the salts [MoO(CNBu(t)())(4)Cl][BPh(4)] (C(4)(v)), [MoO(dmpe)(2)Cl]Cl.5H(2)O (C(2)(v)), and [MoO(PMe(3))(4)Cl][PF(6)] (C(2)(v)()); the lower symmetries of the phosphine derivatives are the result of the steric properties of the phosphine ligands. The Motbd1;O stretching frequencies of these ions (948-959 cm(-)(1)) are essentially insensitive to the nature and geometry of the equatorial ligands. In contrast, the electronic absorption bands arising from the nominal d(xy)() --> d(xz), d(yz) (n --> pi(MoO)) ligand-field transition exhibit a large dependence on the geometry of the equatorial ligands. Specifically, the electronic spectrum of [MoO(CNBu(t)())(4)Cl](+) exhibits a single (1)[n --> pi(xz)(,)(yz)] band, whereas the spectra of both [MoO(dmpe)(2)Cl](+) and [MoO(PMe(3))(4)Cl](+) reveal separate (1)[n --> pi(xz)] and (1)[n --> pi(yz)] bands. A general theoretical model of the n --> pi state energies of structurally distorted d(2) M(triplebondE)L(4)X chromophores is developed in order to interpret the electronic spectra of the phosphine derivatives. Analysis of the n --> pi transition energies using this model indicates that the d(xz) and d(yz) pi(MotriplebondO) orbitals are nondegenerate for the C(2)(v)-symmetry ions and the n --> pi(xz) and n --> pi(yz) excited states are characterized by different two-electron terms. These effects lead to a significant redistribution of intensity between certain spin-allowed and spin-forbidden absorption bands. The applicability of this model to the excited states produced by delta --> pi and pi --> delta symmetry electronic transitions of other chromophores is discussed.

Journal Article↗
PubMed2005

Control of electron acceptor ability with ligands (L) in photoinduced electron transfer from zinc porphyrin or zinc phthalocyanine to [Ru3(mu3-O)(mu-CH3COO)6L3]+.

Photoinduced electron-transfer processes from the excited triplet states of zinc tetraphenylporphyrin (3ZnTPP*) or zinc tetra-tert-butylphthalocyanine (3ZnTBPc*) to oxo-acetato-bridged triruthenium clusters [Ru3(mu3-O)(mu-CH3CO2)6(L)3]+ have been confirmed by nanosecond laser flash photolysis in the visible and near-IR regions. The rise of the transient absorption spectra of the radical cations of ZnTPP and ZnTBPc and the reduced form of the oxo-acetato-bridged triruthenium cluster ([Ru3(mu3-O)(mu-CH3CO2)6(L)3]0) were observed with the concomitant decays of 3ZnTPP* or 3ZnTBPc*. The evaluated rate constants (kET) and quantum yields (PhiET) for electron-transfer were increased with the order of electron-withdrawing ability of the ligands (L) coordinated to the Ru atoms, 4-cyanopyridine > triphenylphosphine > pyridine > 4-(dimethylamino)pyridine, which is the order of promoting the electron-accepting ability of [Ru3(mu3-O)(mu-CH3CO2)6(L)3]+. The PhiET values for 3ZnTPP* were lower than those for 3ZnTBPc*, suggesting the presence of competitive processes such as energy transfer process from 3ZnTPP* to the triplet states of [Ru3(mu3-O)(mu-CH3COO)6(L)3]+. For the back electron-transfer process, second-order kinetics indicates that the radical cations of ZnTPP or ZnTBPc and [Ru3(mu3-O)(mu-CH3COO)6(L)3]0 return to the original system after solvation in polar solvents at a diffusion controlled limit without side reactions, providing reversible photosensitizing intermolecular electron-transfer systems.

Journal Article↗
PubMed2001

Theoretical study of electron, proton, and proton-coupled electron transfer in iron bi-imidazoline complexes.

A comparative theoretical investigation of single electron transfer (ET), single proton transfer (PT), and proton-coupled electron transfer (PCET) reactions in iron bi-imidazoline complexes is presented. These calculations are motivated by experimental studies showing that the rates of ET and PCET are similar and are both slower than the rate of PT for these systems (Roth, J. P.; Lovel, S.; Mayer, J. M. J. Am. Chem. Soc. 2000, 122, 5486). The theoretical calculations are based on a multistate continuum theory, in which the solute is described by a multistate valence bond model, the transferring hydrogen nucleus is treated quantum mechanically, and the solvent is represented as a dielectric continuum. For electronically nonadiabatic electron transfer, the rate expressions for ET and PCET depend on the inner-sphere (solute) and outer-sphere (solvent) reorganization energies and on the electronic coupling, which is averaged over the reactant and product proton vibrational wave functions for PCET. The small overlap of the proton vibrational wave functions localized on opposite sides of the proton transfer interface decreases the coupling for PCET relative to ET. The theory accurately reproduces the experimentally measured rates and deuterium kinetic isotope effects for ET and PCET. The calculations indicate that the similarity of the rates for ET and PCET is due mainly to the compensation of the smaller outer-sphere solvent reorganization energy for PCET by the larger coupling for ET. The moderate kinetic isotope effect for PCET arises from the relatively short proton transfer distance. The PT reaction is found to be dominated by solute reorganization (with very small solvent reorganization energy) and to be electronically adiabatic, leading to a fundamentally different mechanism that accounts for the faster rate.

Journal Article↗
PubMed2004

Electronically-coupled tungsten-tungsten quadruple bonds: comparisons of electron delocalization in 3,6-dioxypyridazine and oxalate-bridged compounds.

The preparation of the 3,6-dioxypyridazine-bridged tungsten complex, [W(2)(O(2)C(t)Bu)(3)](2)(mu-H(2)C(4)N(2)O(2)), I, is described, along with its single-electron oxidized cation, I(+), formed in the reaction between I and Ag(+)PF(6)(-). Compound I has been structurally characterized as a PPh(3) adduct, and I(+)PF(6)(-) as a THF solvate, by single-crystal X-ray studies. The geometric parameters of these compounds compare well with those calculated for the model compounds [W(2)(O(2)CH)(3)](2)(mu-H(2)C(4)N(2)O(2)) and [W(2)(O(2)CH)(3)](2)(micro-H(2)C(4)N(2)O(2))(+) by density functional theory employing the Gaussian 98 and 03 suite of programs. The calculations indicate that the two W(2) centers are strongly coupled by M(2) delta-to-bridge pi-bonding, and further coupled by direct M(2)...M(2) bonding. Compound I is purple and shows an intense absorption in the visible region due to a metal-to-bridge charge transfer and, with excitation within this absorption, compound I exhibits pronounced resonance Raman bands associated with symmetric vibrations of the bridge and the M(4) unit. The cyclic voltammogram of I in THF, the EPR spectrum of I(+)PF(6) in 2-MeTHF and the electronic absorption spectrum of I(+)PF(6)(-) in THF are consistent with electron delocalization over both W(2) units. These new data are compared with previous data for the molybdenum analogue, related oxalate-bridged compounds and closely related cyclic polyamidato-bridged Mo(4)-containing compounds. It is proposed that, while the electronic coupling occurs principally by an electron-hopping mechanism for oxalate-bridged compounds, hole-hopping contributes significantly in the cases of the amidate bridges and that this is more important for M = Mo than for M = W. Furthermore, for Class III fully delocalized mixed-valence compounds, the magnitude of K(c), determined from electrochemical methods, is not necessarily a measure of the extent of electron delocalization.

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