Electric spin resonance spectroscopy

The physical properties of bis(dithiocarbamate) complexes have also been exploited by Bmce and co-workers (1485,1668) to generate a series of paramagnetic mesomorphic liquid crystals, showing smectic phases Sc and crystal p mesophases. Electric spin resonance spectroscopy has shown the existence of a long-range exchange interaction at all temperatures, as established by the collapse of the hyperfine structure in the spectra of the condensed samples. Further, a comparison of the principal g-values in the solid state and in solution indicates that in the solid the molecules pack with their molecular axes parallel (1668). 

Spectroelectrochemistry encompasses a group of techniques that allow simultaneous acquisition of electrochemical and spectroscopic information in situ in an electrochemical cell. A wide range of spectroscopic techniques may be combined with electrochemistry, including electronic (UV-visible) absorption and reflectance spectroscopy, luminescence spectroscopy, infrared and Raman spectroscopies, electron spin resonance spectroscopy and ellipsometry. Molecular properties such as molar absorption coefficients, vibrational absorption frequencies and electronic or magnetic resonance frequencies, in addition to electrical parameters such as current, voltage or charge, are now being used routinely for the study of electron transfer reaction pathways and the fundamental molecular states at interfaces. In this article the principles and practice of electronic spectroelectrochemistry are introduced. 

In 1968/1969 DaH Olio et al. in Parma, Italy, revitalized polypyrrole chemistry by oxidizing pyrrole itself electrolytically to pyrrole black ("noir d oxypyrrol")/° In contrast to the investigations of Weiss et al., Dall Olio and his coauthors focused on the electrochemical behavior of pyrrole and its electropolymerization. The paramagnetic behavior of the polymer was studied (the g-factor of the free radical was measured to 2.0026 by electron spin resonance spectroscopy), and a remarkable electric conductivity of 7.54 S/cm at ambient temperature was foimd. 

Quadrupole coupling constants for molecules are usually determined from the hyperfine structure of pure rotational spectra or from electric-beam and magnetic-beam resonance spectroscopies. Nuclear magnetic resonance, electron spin resonance and Mossbauer spectroscopies are also routes to the property. There is a large amount of experimental data for and halogen-substituted molecules. Less data is available for deuterium because the nuclear quadrupole is small. 

Thanks to the extensive literature on Aujj and the related smaller gold cluster compounds, plus some new results and reanalysis of older results to be presented here, it is now possible to paint a fairly consistent physical picture of the AU55 cluster system. To this end, the results of several microscopic techniques, such as Extended X-ray Absorption Fine Structure (EXAFS) [39,40,41], Mossbauer Effect Spectroscopy (MES) [24, 25, 42,43,44,45,46], Secondary Ion Mass Spectrometry (SIMS) [35, 36], Photoemission Spectroscopy (XPS and UPS) [47,48,49], nuclear magnetic resonance (NMR) [29, 50, 51], and electron spin resonance (ESR) [17, 52, 53, 54] will be combined with the results of several macroscopic techniques, such as Specific Heat (Cv) [25, 54, 55, 56,49], Differential Scanning Calorimetry (DSC) [57], Thermo-gravimetric Analysis (TGA) [58], UV-visible absorption spectroscopy [40, 57,17, 59, 60], AC and DC Electrical Conductivity [29,61,62, 63,30] and Magnetic Susceptibility [64, 53]. This is the first metal cluster system that has been subjected to such a comprehensive examination. 

Electric-quadrupole transition, 123,127 Electromagnetic radiation, 114-117. See also Radiation, electromagnetic Electromagnetic spectrum, 115 Electronic energy, 57,64,148 Electronic spectra, 130, 296-314 of diatomics, 298-306 and molecular structure, 311 of polyatomics, 71-72, 73, 75, 306-314 selection rules for, 297-301, 306-307 Electronic structure of molecules, 56-76 Electron spectroscopy for chemical analysis (ESCA), 319-320 Electron spin resonance (ESR), 130, 366-381... 

Methods such as nuclear magnetic resonance (NMR), electron spectroscopy for chemical analysis (ESCA), electron spin resonance (ESR), infrared (IR), and laser raman spectroscopy could be used in conjunction with rate studies to define mechanisms. Another alternative would be to use fast kinetic techniques such as pressure-jump relaxation, electric field pulse, or stopped flow (Chapter 4), where chemical kinetics are measured and mechanisms can be definitively established. 

The direct synthesis by anodic oxidation of a new series of electrically conducting poljnners is described.. Our polymers derive from sulfur and/or nitrogen containing hetero-cycles such as 2-(2-thienyl)pyrrole, thiazole, indole, and phthalazine. The anodic oxidation of these monomers is carried out in acetonitrile solutions containing tetrabu-tylammonium salts (TBA X ) ith X = BF, tetraethylammonium salt, TEA H C-C H -S0. Characterization of the materials by electrical conductivity, electron spin resonance, uv-visible spectroscopy, and cyclic voltammetry is discussed. 

Methods of Characterization The polymers were characterized by four-probe electrical conductivity measurements between room temperature and liquid nitrogen, electron spin resonance (Varlan E-line series), scanning electron microscopy (Hitachi 520), cyclic voltammetry (Princeton Applied Research Instruments), and uv-vlsl-ble spectroscopy (Perkin Elmer 330). 

In crystals, impurities can take simple configurations. But depending on their concentration, diffusion coefficient, or chemical properties and also on the presence of different kind of impurities or of lattice defects, more complex situations can be found. Apart from indirect information like electrical measurements or X-ray diffraction, methods such as optical spectroscopy under uniaxial stress, electron spin resonance, channelling, positron annihilation or Extended X-ray Absorption Fine Structure (EXAFS) can provide more detailed results on the location and atomic structure of impurities and defects in crystals. Here, we describe the simplest atomic structures more complicated structures are discussed in other chapters. To explain the locations of the impurities and defects whose optical properties are discussed in this book, an account of the most common crystal structures mentioned is given in Appendix B. 

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