Molecular structures of 3-hydroxybenzoic acid and 4-hydroxybenzoic acid, obtained by gas-phase electron diffraction and theoretical calculations

The structures of 3-hydroxybenzoic acid and 4-hydroxybenzoic acid have been determined by gas-phase electron diffraction using results from quantum chemical calculations to inform the choice of restraints applied to some of the structural parameters. The results from the study presented here demonstrate that resonance hybrids are not as helpful in rationalizing the structures of 2-, 3-, and 4-hydroxybenzoic acids as are models based upon electrostatic effects.

Electronic transitions and bonding properties in a series of five-coordinate “16-electron” complexes [Mn(CO)3(L2)]− (L2=chelating redox-active π-donor ligand)

In this article we present for the first time accurate density functional theory (DFT) and time-dependent (TD) DFT data for a series of electronically unsaturated five-coordinate complexes [Mn(CO)(3)(L-2)](-), where L-2 stands for a chelating strong pi-donor ligand represented by catecholate, dithiolate, amidothiolate, reduced alpha-diimine (1,4-dialkyl-1,4-diazabutadiene (R-DAB), 2,2'-bipyridine) and reduced 2,2'-biphosphinine types. The single-crystal X-ray structure of the unusual compound [Na(BPY)][Mn(CO)(3)(BPY)]center dot Et2O and the electronic absorption spectrum of the anion [Mn(CO)(3)(BPY)](-) are new in the literature. The nature of the bidentate ligand determines the bonding in the complexes, which varies between two limiting forms: from completely pi-delocalized diamagnetic {(CO)(3)Mn-L-2}(-) for L-2 = alpha-diimine or biphosphinine, to largely valence-trapped {(CO)(3)Mn-1-L-2(2-)}(-) for L-2(2-) = catecholate, where the formal oxidation states of Mn and L-2 can be assigned. The variable degree of the pi-delocalization in the Mn(L-2) chelate ring is indicated by experimental resonance Raman spectra of [Mn(CO)(3)(L-2)](-) (L-2=3,5-di-tBu-catecholate and iPr-DAB), where accurate assignments of the diagnostically important Raman bands have been aided by vibrational analysis. The L-2 = catecholate type of complexes is known to react with Lewis bases (CO substitution, formation of six-coordinate adducts) while the strongly pi-delocalized complexes are inert. The five-coordinate complexes adopt usually a distorted square pyramidal geometry in the solid state, even though transitions to a trigonal bipyramid are also not rare. The experimental structural data and the corresponding DFT-computed values of bond lengths and angles are in a very good agreement. TD-DFT calculations of electronic absorption spectra of the studied Mn complexes and the strongly pi-delocalized reference compound [Fe(CO)(3)(Me-DAB)] have reproduced qualitatively well the experimental spectra. Analyses of the computed electronic transitions in the visible spectroscopic region show that the lowest-energy absorption band always contains a dominant (in some cases almost exclusive) contribution from a pi(HOMO) -> pi*(LUMO) transition within the MnL2 metallacycle. The character of this optical excitation depends strongly on the composition of the frontier orbitals, varying from a partial L-2 -> Mn charge transfer (LMCT) through a fully delocalized pi(MnL2) -> pi*(MnL2) situation to a mixed (CO)Mn -> L-2 charge transfer (LLCT/MLCT). The latter character is most apparent in the case of the reference complex [Fe(CO)(3)(Me-DAB)]. The higher-lying, usually strongly mixed electronic transitions in the visible absorption region originate in the three lower-lying occupied orbitals, HOMO - 1 to HOMO - 3, with significant metal-d contributions. Assignment of these optical excitations to electronic transitions of a specific type is difficult. A partial LLCT/MLCT character is encountered most frequently. The electronic absorption spectra become more complex when the chelating ligand L-2, such as 2,2'-bipyridine, features two or more closely spaced low-lying empty pi* orbitals.

A hydrogen-1 nuclear magnetic resonance, mass spectral and extended Hückel study of some olefin complexes of rhodium(I) and iridium(I) and the crystal and molecular structure of η4-2,4-dimethylpenta-1,4-diene(η5-formylcyclopentadienyl)rhodium(I)

A 1H NMR study of monosubstituted η-cyclopentadienyl-rhodium(I) complexes of type LLRh(C5H4X) and -iridium(I) complexes of type L2Ir(C5H4X) (L = ethene, LL = 1,3- or 1,5-diolefin; X = C(C6H5)3, CHO, or COOCH3) has been carried out. For complexes of both metals in which the neutral ligand is ethene or a non-conjugated diolefin the NMR spectra of the cyclopentadienyl protons are unusual in that H(2), H(5) resonate to high field either at room temperature or below. The corresponding NMR spectra for the cyclopentadienyl ring protons of complexes where the neutral ligand is a conjugated diene are, with one exception, normal. A single crystal X-ray structural analysis of (η4-2,4-dimethylpenta-1,4-diene)(η5-formylcyclopentadienyl)rhodium(I) (which exhibits an abnormal 1H NMR spectrum) reveals substantial localisation of electron density in the C(3)C(4) Cp ring bond (1.283(33) Å) which may be consistent with a contribution from an ‘allyl-ene’ rotamer to the ring—metal bonding scheme. An extended Hückel calculation with self consistent charge iteration was performed on this complex. The results predict a greater Mulliken overlap population for the C(3)C(4) bond in the cyclopentadienyl ring and show that the localisation is dependent on both the Cp ring substituent and the nature of the diolefin. The mass spectral fragmentation patterns of some representative diene complexes of iridium(I) and rhodium(I) are presented.

Electron acceleration and parallel electric fields due to kinetic Alfvén waves in plasma with similar thermal and Alfvén speeds

We investigate electron acceleration due to shear Alfven waves in a collissionless plasma for plasma parameters typical of 4–5RE radial distance from the Earth along auroral field lines. Recent observational work has motivated this study, which explores the plasma regime where the thermal velocity of the electrons is similar to the Alfven speed of the plasma, encouraging Landau resonance for electrons in the wave fields. We use a self-consistent kinetic simulation model to follow the evolution of the electrons as they interact with a short-duration wave pulse, which allows us to determine the parallel electric field of the shear Alfven wave due to both electron inertia and electron pressure effects. The simulation demonstrates that electrons can be accelerated to keV energies in a modest amplitude sub-second period wave. We compare the parallel electric field obtained from the simulation with those provided by fluid approximations.

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.

Magnetic resonance and conductivity study of gelatin-based proton conductor polymer electrolytes

This work report results from proton nuclear magnetic resonance (NMR), continuous-wave (CW-EPR) and pulsed electron paramagnetic resonance (P-EPR) and complex impedance spectroscopy of gelatin-based polymer gel electrolytes containing acetic acid. cross-linked with formaldehyde and plasticized with glycerol. Ionic conductivity of 2 x 10(-5) S/cm was obtained at room temperature for samples prepared with 33 wt% of acetic acid. Proton ((1)H) line shapes and spin-lattice relaxation times were measured as a function of temperature. The NMR results show that the proton mobility is dependent on acetic acid content in the plasticized polymer gel electrolytes. The CW-EPR spectra, which were carried out in samples doped with copper perchlorate, indicate the presence of the paramagnetic Cu(2+) ions in axially distorted sites. The P-EPR technique, known as electron spin echo envelope modulation (ESEEM), was employed to show the involvement of both, hydrogen and nitrogen atoms, in the copper complexation of the gel electrolyte. (C) 2009 Elsevier Ltd. All rights reserved.

Magnetic resonance study of a vanadium pentoxide gel

In this work we report results from continuous-wave (CW) and pulsed electron paramagnetic resonance (EPR) and proton nuclear magnetic resonance (NMR) studies of the vanadium pentoxide xerogel V2O5:nH(2)O (n approximate to 1.6). The low temperature CW-EPR spectrum shows hyperfine structure due to coupling of unpaired V4+ electron with the vanadium nucleus. The analysis of the spin Hamiltonian parameters suggests that the V4+ ions are located in tetragonally distorted octahedral sites. The transition temperature from the rigid-lattice low-temperature regime to the high temperature liquid-like regime was determined from the analysis of the temperature dependence of the hyperfine splitting and the V4+ motional correlation time. The Electron Spin Echo Envelope Modulation (ESEEM) data shows the signals resulting from the interaction of H-1 nuclei with V4+ ions. The modulation effect was observed only for field values in the center of the EPR absorption spectrum corresponding to the single crystals orientated perpendicular to the magnetic field direction. At least three protons are identified in the xerogel by our magnetic resonance experiments: (I) the OH groups in the equatorial plane, (ii) the bound water molecules in the axial V=O bond and (iii) the free mobile water molecules between the oxide layers. Proton NMR lineshapes and spin-lattice relaxation times were measured in the temperature range between 150 K and 323 K. Our analysis indicates that only a fraction of the xerogel protons contribute to the measured conductivity.

Fano resonance in heavily doped porous silicon

Unexpectedly, the Fano resonance caused by the interference of continuum electron excitations with the longitudinal optical (LO) phonons was observed in random porous Si by Raman scattering. The analysis of the experimental data shows that the electron states trapped at the Si-SiO(2) interface dominate in the observed Raman scattering. The gap energy associated with the interface states was determined. Copyright (C) 2011 John Wiley & Sons, Ltd.

Bichromophoric behavior of nitrophenyl-triazene anions: a resonance Raman spectroscopy investigation

Highly delocalized molecular frameworks with intense charge transfer transitions, known as push-pull systems, are of central interest in many areas of chemistry, as is the case of nitrophenyl-triazene derivatives. The 1,3-bis(2-nitrophenyl)triazene and 1,3-bis(4-nitrophenyl)triazene were investigated by electronic (UV-Vis) and resonance Raman (RR) spectroscopies. The bichromophoric behavior of 1,3-bis(4-nitrophenyl)triazene anion opens the possibility of tuning with visible radiation, two distinct electronic states. The RR profiles of nitrophenyl-triazene derivatives clearly show that the first allowed electronic state can be assigned to a charge transfer from the ring pi system to the NO2 moiety (ca 520 nm), while the second, as a charge transfer from N-3(-) to the aromatic ring (ca 390 nm). In the para-substituted derivative, a more efficient electron transfer and a greater energy separation between the two excited states are observed. Copyright (C) 2008 John Wiley & Sons, Ltd.

The electronic delocalization in para-substituted beta-nitrostyrenes probed by resonance Raman spectroscopy and quantum-chemical calculations

The electronic (UV-vis) and resonance Raman (RR) spectra of a series of para-substituted trans-beta-nitrostyrenes were investigated to determine the influence of the electron donating properties of the substituent (X = H, NO2, COOH, Cl, OCH3, OH, N(CH3)(2), and O-) on the extent of the charge transfer to the electron-withdrawing NO2 group directly linked to the ethylenic (C=C) unit. The Raman spectra and quantum chemical calculations show clearly the correlation of the electron donating power of the X group with the wavenumbers of the nu(s)(NO2) and nu (C=C)(sty) normal modes. In conditions of resonance with the lowest excited electronic state, one observes for X = OH and N(CH3)2 that the symmetric stretching of the NO2. nu(s)(NO2), is the most substantially enhanced mode, whereas for X = O-, the chromophore is extended over the whole molecule, with substantial enhancement of several carbon backbone modes. Copyright (c) 2008 John Wiley & Sons, Ltd.

Non-Zeeman splitting for a spin-resolved STM with a Kondo adatom in a spin-polarized two-dimensional electron gas

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Electrically detected and conventional magnetic resonance investigation of surface and bulk states in polyaniline thin films

Electrically detected magnetic resonance (EDMR) and electron paramagnetic resonance (EPR) were used to investigate emeraldine base polyaniline films. The magnetic susceptibility presented a Curie (localized spins)-Pauli (delocalized spins) transition at 240 K, when we also observed a transition in the dependence of the g factor with temperature (T). Peak-to-peak linewidth decreases with increasing temperature, reflecting that motional narrowing limits the hyperfine and dipolar broadening in this polymer. EDMR spectra could only be observed above 250 K in accordance to EPR results. Surface and bulk transport could be separated and their analysis reflected the effect of magnetic interaction with oxygen. (c) 2007 American Institute of Physics.

Magnetic resonance study of the crystallization behavior of InF3-based glasses doped with Cu2+, Mn2+ and Gd3+

The crystallization of fluoroindate glasses doped with Gd3+, Mn2+ and Cu2+ heat treated at different temperatures, ranging from the glass transition temperature (Tg) to the crystallization temperature (Tc), are investigated by electron paramagnetic resonance (EPR) and 19F nuclear magnetic resonance (NMR). The EPR spectra indicate that the Cu2+ ions in the glass are located in axially distorted octahedral sites. In the crystallized glass, the g-values agreed with those reported for Ba2ZnF6, which correspond to Cu2+ in a tetragonal compressed F- octahedron and to Cu2+ on interstitial sites with a square-planar F- co-ordination. The EPR spectra of the Mn2+ doped glasses exhibit a sextet structure due to the Mn2+ hyperfine interaction. These spectra suggest a highly ordered environment for the Mn2+ ions (close to octahedral symmetry) in the glass. The EPR spectra of the recrystallized sample exhibit resonances at the same position, suggesting that the Mn2+ ions are located in sites of highly symmetric crystalline field. The increase of the line intensity of the sextet and the decrease of the background line in the thermal treated samples suggest that the Mn2+ ions move to the highly ordered sites which contribute to the sextet structure. The EPR spectra of the Gd3+ doped glasses exhibit the typical U-spectrum of a s-state ion in a low symmetry site in disordered systems. The EPR of the crystallized glasses, in contrast, have shown a strong resonance in g ≈ 2.0, suggesting Gd3+ ions in environment close to cubic symmetry. The 19F NMR spin-lattice relaxation rates were also strongly influenced by the crystallization process that takes over in samples annealed above Tc. For the glass samples (doped or undoped) the 19F magnetization recoveries were found to be adjusted by an exponential function and the spin-lattice relaxation was characterized by a single relaxation time. In contrast, for the samples treated above Tc, the 19F magnetization-recovery becomes non-exponential. A remarkable feature of our results is that the changes in the Cu2+, Mn2+, Gd3+ EPR spectra and NMR relaxation, are always observed for the samples annealed above Tc. © 2006 Elsevier B.V. All rights reserved.

Antiferromagnetic resonance of polycrystalline BiMn2O5

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Flattening of the resonance spectrum of hadrons from κ-deformed Poincaré algebra

Recently Lukierski et al. [1] defined a κ-deformed Poincaré algebra which is characterized by having the energy-momentum and angular momentum sub-algebras not deformed. Further Biedenharn et al. [2] showed that on gauging the κ-deformed electron with the electromagnetic field, one can set a limit on the allowed value of the deformation parameter ∈ ≡ 1/κ < 1 fm. We show that one gets Regge like angular excitations, J, of the mesons, non-strange and strange baryons, with a value of ∈ ∼ 0.082 fm and predict a flattening with J of the corresponding trajectories. The Regge fit improves on including deformation, particularly for the baryon spectrum.