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At least 991 records · Page 55Linked to original sources
PubMed2005

Structure of radical cations of saturated heterocyclic compounds with two heteroatoms as studied by electron paramagnetic resonance, electron-nuclear double resonance, and density functional theory calculations.

The radical cations of piperazine, morpholine, thiomorpholine, and thioxane were investigated by electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy in a solid Freon matrix. Optimized geometry and magnetic parameters of the radical cations were calculated using a density functional theory (DFT)/Perdew-Burke-Ernzerhof (PBE) method. Both experimental and theoretical results suggest that all the studied species adopt chair (or distorted chair) conformations. No evidence for the boat conformers with intramolecular sigma-bonding between heteroatoms were obtained. In the cases of morpholine and thioxane, the oxygen atoms are characterized by relatively small spin populations, whereas a major part of spin density is located at N and S atoms, respectively. The thiomorpholine radical cation exhibits nearly equal spin population of N and S atoms. In most cases (except for thioxane), the calculated magnetic parameters agree with the experimental data reasonably well.

Journal Article↗
PubMed2006

Sub-nanometer Au monolayer-protected clusters exhibiting molecule-like electronic behavior: quantitative high-angle annular dark-field scanning transmission electron microscopy and electrochemical characterization of clusters with precise atomic stoichiometry.

The synthesis and characterization of the clusters Au13[PPh3]4[S(CH2)11CH3]2Cl2 (1) and Au13[PPh3]4[S(CH2)11CH3]4 (2) are described. These mixed-ligand, sub-nanometer clusters, prepared via exchange of dodecanethiol onto phosphine-halide gold clusters, show enhanced stability relative to the parent. The characterization of these clusters features the precise determination of the number of gold atoms in the cluster cores using high-angle annular dark-field scanning transmission electron microscopy, allowing the assignment of 13 gold atoms (+/-3 atoms) to the composition of both cluster molecules. Electrochemical and optical measurements reveal discrete molecular orbital levels and apparent energy gaps of 1.6-1.7 eV for the two cluster molecules. The electrochemical measurements further indicate that the Au13[PPh3]4[S(CH2)11CH3]2Cl2 cluster undergoes an overall two-electron reduction. The electrochemical and spectroscopic properties of the two Au13 cluster molecules are compared with those of a secondary synthetic product, which proved to be larger Au thiolate-derivatized monolayer-protected clusters with an average core of Au180. The latter shows behavior fully consistent with the adoption of metallic-like properties.

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PubMed2005

Visible light decomposition of ammonia to dinitrogen by a new visible light photocatalytic system composed of sensitizer (Ru(bpy)(3)2+), electron mediator (methylviologen) and electron acceptor (dioxygen).

Visible light decomposition of aqueous ammonia to dinitrogen was successfully achieved by using a new photocatalytic system based on a molecular photoelectron relay composed of a sensitizer (Ru(bpy)(3)2+), an electron mediator (methylviologen) and an electron acceptor (dioxygen), which can be used as a visible light-driven photocatalyst instead of UV-driven semiconductors.

Journal Article↗
PubMed2005

Butane-1,4-diyl dications stabilized by steric factors: electrochiroptical response systems based on reversible interconversion between dihydro[5]helicene-type electron acceptors and electron-donating 1,1'-binaphthyls.

Incorporation in the dihydro[5]helicene framework prevents deprotonation of the title dications by steric factors, thus allowing their isolation as deeply colored stable salts. Based on the reversible interconversion with the electron-donating binaphthylic diolefins, they constitute a new class of electrochromic systems, in which C-C bond making/breaking is accompanied by two-electron transfer. Optically pure (R)-binaphthylic donors are interconvertible with the 1,4-dications with the R,R-configuration. The very large molar ellipticity makes it possible for them to be used as electrochiroptical response systems, by which the electrochemical input is transduced into two spectral outputs, i.e. UV-Vis and circular dichroism. Structurally related push-pull-type bis(quinonemethide)s also exhibit a similar multi-output electrochemical response.

Journal Article↗
PubMed2006

Structural consequences of the one-electron reduction of d4 [Mo(CO)2(eta-PhC[triple bond]CPh)Tp']+ and the electronic structure of the d5 radicals [M(CO)L(eta-MeC[triple bond]CMe)Tp'] {L = CO and P(OCH2)3CEt}.

Reduction of [M(CO)2(eta-RC[triple bond]CR')Tp']X {Tp' = hydrotris(3,5-dimethylpyrazolyl)borate, M = Mo, X = [PF6]-, R = R' = Ph, C6H4OMe-4 or Me; R = Ph, R' = H; M = W, X = [BF4]-, R = R' = Ph or Me; R = Ph, R' = H} with [Co(eta-C5H5)2] gave paramagnetic [M(CO)2(eta-RC[triple bond]CR')Tp'], characterised by IR and ESR spectroscopy. X-Ray structural studies on the redox pair [Mo(CO)2(eta-PhC[triple bond]CPh)Tp'] and [Mo(CO)2(eta-PhC[triple bond]CPh)Tp'][PF6] showed that oxidation is accompanied by a lengthening of the C[triple bond]C bond and shortening of the Mo-C(alkyne) bonds, consistent with removal of an electron from an orbital antibonding with respect to the Mo-alkyne bond, and with conversion of the alkyne from a three- to a four-electron donor. Reduction of [Mo(CO)(NCMe)(eta-MeC[triple bond]CMe)Tp'][PF6] with [Co(eta-C5H5)2] in CH2Cl2 gives [MoCl(CO)(eta-MeC[triple bond]CMe)Tp'], via nitrile substitution in [Mo(CO)(NCMe)(eta-MeC[triple bond]CMe)Tp'], whereas a similar reaction with [M(CO){P(OCH2)3CEt}(eta-MeC[triple bond]CMe)Tp']+ (M = Mo or W) gives the phosphite-containing radicals [M(CO){P(OCH2)3CEt}(eta-MeC[triple bond]CMe)Tp']. ESR spectroscopic studies and DFT calculations on [M(CO)L(eta-MeC[triple bond]CMe)Tp'] {M = Mo or W, L = CO or P(OCH2)3CEt} show the SOMO of the neutral d5 species (the LUMO of the d4 cations) to be largely d(yz) in character although much more delocalised in the W complexes. Non-coincidence effects between the g and metal hyperfine matrices in the Mo spectra indicate hybridisation of the metal d-orbitals in the SOMO, consistent with a rotation of the coordinated alkyne about the M-C2 axis.

Journal Article↗
PubMed2006

Electronic structures of intermolecular charge-transfer states in fast electron transfers with tetrathiafulvalene donor. Thermal and photoactivation of [2 + 4] cycloaddition to o-chloranil acceptor.

Tetrathiafulvalene (TTF) spontaneously forms a series of unusual charge-transfer complexes with various quinonoid acceptors such as o-chloranil (CA) that show pronounced near-IR absorption (lambda(CT) = 1100 nm). The successful isolation of the corresponding [1 : 1] donor-acceptor complex from solution and X-ray crystallographic analysis at low temperatures reveal the polarized charge-transfer state: [TTF(q+),CA(q-)] with high degree of charge-transfer (q = 0.6), which is spectrally and crystallographically distinguished from the separate redox (ion-pair) state: [TTF(+*) + CA(-*) ]. The unique interconversion of charge-transfer and electron-transfer states is theoretically well-accommodated by Mulliken theory using semi-empirical valence-bond and molecular-orbital methodologies. Mechanistic implications are discussed of both the thermally activated and the photochemically promoted processes via fast (intracomplex) electron transfer followed by collapse of the adiabatic and the non-adiabatic (vibrationally-excited) ion-pairs, respectively, to the [2 + 4] cycloadduct of tetrathiafulvalene and o-chloranil.

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PubMed2001

Electron energy-loss near-edge structure -- a tool for the investigation of electronic structure on the nanometre scale.

Electron energy-loss near-edge structure (ELNES) is a technique that can be used to measure the electronic structure (i.e. bonding) in materials with subnanometre spatial resolution. This review covers the theoretical principles behind the technique, the experimental procedures necessary to acquire good ELNES spectra, including potential artefacts, and gives examples relevant to materials science.

Journal Article↗
PubMed2005

Electronically forbidden (5sigmau-->ksigmau) photoionization of CS2: mode-specific electronic-vibrational coupling.

Vibrationally resolved photoelectron spectroscopy of the CS(2) (+)(B (2)Sigma(u) (+)) state is used to show how nontotally symmetric vibrations "activate" a forbidden electronic transition in the photoionization continuum, specifically, a 5sigma(u)-->ksigma(u) shape resonance, that would be inaccessible in the absence of a symmetry breaking vibration. This electronic channel is forbidden owing to inversion symmetry selection rules, but it can be accessed when a nonsymmetric vibration is excited, such as bending or antisymmetric stretching. Photoelectron spectra are acquired for photon energies 17</=hnu</=72 eV, and it is observed that the forbidden vibrational transitions are selectively enhanced in the region of a symmetry-forbidden continuum shape resonance centered at hnu approximately 42 eV. Schwinger variational calculations are performed to analyze the data, and the theoretical analysis demonstrates that the observed forbidden transitions are due to photoelectron-mediated vibronic coupling, rather than interchannel Herzberg-Teller mixing. We observe and explain the counterintuitive result that some vibrational branching ratios vary strongly with energy in the region of the resonance, even though the resonance position and width are not appreciably influenced by geometry changes that correspond to the affected vibrations. In addition, we find that another resonant channel, 5sigma(u)-->kpi(g), influences the symmetric stretch branching ratio. All of the observed effects can be understood within the framework of the Chase adiabatic approximation, i.e., the Born-Oppenheimer approximation applied to photoionization.

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PubMed2005

The electronic structure of free water clusters probed by Auger electron spectroscopy.

(H2O)(N) clusters generated in a supersonic expansion source with N approximately 1000 were core ionized by synchrotron radiation, giving rise to core-level photoelectron and Auger electron spectra (AES), free from charging effects. The AES is interpreted as being intermediate between the molecular and solid water spectra showing broadened bands as well as a significant shoulder at high kinetic energy. Qualitative considerations as well as ab initio calculations explain this shoulder to be due to delocalized final states in which the two valence holes are mostly located at different water molecules. The ab initio calculations show that valence hole configurations with both valence holes at the core-ionized water molecule are admixed to these final states and give rise to their intensity in the AES. Density-functional investigations of model systems for the doubly ionized final states--the water dimer and a 20-molecule water cluster--were performed to analyze the localization of the two valence holes in the electronic ground states. Whereas these holes are preferentially located at the same water molecule in the dimer, they are delocalized in the cluster showing a preference of the holes for surface molecules. The calculated double-ionization potential of the cluster (22.1 eV) is in reasonable agreement with the low-energy limit of the delocalized hole shoulder in the AES.

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PubMed2006

Basis set limit electronic excitation energies, ionization potentials, and electron affinities for the 3d transition metal atoms: Coupled cluster and multireference methods.

Recently developed correlation consistent basis sets for the first row transition metal elements Sc-Zn have been utilized to determine complete basis set (CBS) scalar relativistic electron affinities, ionization potentials, and 4s(2)3d(n-2)-4s(1)d(n-1) electronic excitation energies with single reference coupled cluster methods [CCSD(T), CCSDT, and CCSDTQ] and multireference configuration interaction with three reference spaces: 3d4s, 3d4s4p, and 3d4s4p3d'. The theoretical values calculated with the highest order coupled cluster techniques at the CBS limit, including extrapolations to full configuration interaction, are well within 1 kcal/mol of the corresponding experimental data. For the early transition metal elements (Sc-Mn) the internally contracted multireference averaged coupled pair functional method yielded excellent agreement with experiment; however, the atomic properties for the late transition metals (Mn-Zn) proved to be much more difficult to describe with this level of theory, even with the largest reference function of the present work.

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PubMed1987

Formation of three-electron bonds in one-electron oxidized methionine dipeptides: a pulse radiolytic study.

One electron oxidation of methionine dipeptides (Met-X and X-Met, where X = Gly or Ser) was carried out using the pulse radiolysis technique. It was apparent that the mode of oxidative action of OH radicals on methionine dipeptides was governed by the sequence of amino acids. Spectral evidence suggests that an intramolecular three-electron bond between nitrogen and sulphur atoms is not formed if these two atoms are separated by a peptide bond.

Dipeptides↗
PubMed2000

Laser-driven electron cyclotron autoresonance accelerator with production of an optically chopped electron beam.

Analysis is presented of the gyroresonant acceleration of electrons in a vacuum using a focused laser. Continuous and equal acceleration is shown for electrons injected at all optical phases over an interaction length of tens of centimeters. Beam stalling is avoided as beam energy increases. Acceleration from 50 to 178 MeV is predicted for a 4 TW, 10.6-microm laser focused to a waist radius of 1.0 mm; these parameters correspond to a planned experiment. A beam stop with an off-axis hole after acceleration is shown to create a train of optically chopped bunches with 3-fs bunch lengths and a 35-fs period.

Journal Article↗
PubMed2000

Electronic resonance and symmetry in single-molecule inelastic electron tunneling

Inelastic electron tunneling spectroscopy and microscopy with a scanning tunneling microscope revealed two vibrational modes showing a decrease in conductance at +/-82.0 and +/-38.3 mV sample bias for single oxygen molecules chemisorbed on the fourfold hollow sites of Ag(110) surface at 13 K. The spatial distribution of the vibrational intensities exhibited pi(g)-orbital (perpendicular to surface) symmetry of O2 with the molecular axis along the [001] direction. These results are attributed to resonant inelastic electron tunneling.

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PubMed2000

New mechanism for electron emission from planar cold cathodes: the solid-state field-controlled electron emitter

A new mechanism for electron emission from planar cathodes is described. The theoretical analysis shows that, with an ultrathin wide band-gap semiconductor layer (UTSC) on a metal, the surface barrier is lowered to approximately 0.1 eV due to the creation of a space charge induced by the electrons injected from the metal. The barrier height depends mostly on the UTSC thickness and not on the state of the surface, as in thermionic and field emissions. This mechanism explains the measured stable emission at 300 K and 10(-7) Torr, with a threshold field of only approximately 50 V/&mgr;m, from these solid-state field-controlled emitters.

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PubMed2004

Electron thermal diffusivity due to the electron temperature gradient mode.

Charge neutrality breaks down in the short wavelength toroidal electron temperature gradient mode. In contrast to the ion temperature gradient mode, the wave number normalized by the Debye wave number, k/k(De), appears as a natural scale parameter, rather than the finite Larmor radius parameter k( perpendicular )rho(e). The growth rate and consequent mixing length estimate yields an electron thermal diffusivity large enough to be relevant to tokamaks.

Journal Article↗
PubMed2004

Interference effect in electron emission in heavy ion collisions with h2 detected by comparison with the measured electron spectrum from atomic hydrogen.

Direct evidence of the interference effect in the electron emission spectra from ionization of molecular hydrogen in collisions with bare C and F ions at relatively low collision energies is presented. Oscillations due to the interference are deduced by comparing the measured double differential cross sections of the electrons emitted from molecular hydrogen to those emitted from atomic hydrogen, rather than using the calculated cross sections for H as in a previous report. We believe these experimental data provide stronger support for the evidence of the interference effect. We show that it is not only a feature of very high energy collisions, but also a feature to be observed in relatively lower energy collisions.

Journal Article↗
PubMed2004

Two-dimensional electron-hole liquid in single Si quantum wells with large electronic and dielectric confinement.

We report a luminescence study of the electronic properties of the 2D electron-hole liquid in crystalline Si quantum wells with SiO2 dielectric barriers. The Fermi-Dirac condensation of e-h pairs into a metallic liquid is strongly enhanced by spatial localization. We present experimental evidence for the formation of liquid nanodroplets, with size increasing with e-h pair density. The quantum confined regime is observed for well width below 15 nm. The data are analyzed in a confinement model that takes account of the band-gap renormalization by 2D many-body effects and the increase of the Coulomb interactions due to the dielectric mismatch between the Si well and the SiO2 barriers.

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