Crystal Physics, Diffraction, Theoretical and General Crystallography

A formula has been derived for the mean-square error in the phases of crystal reflections determined through the multiwavelength anomalous scattering method. The error is written in terms of a simple function of the positions in the complex plane of the 'centres' corresponding to the different wavelengths. For the case of three centres, the mean-square error is inversely proportional to the area of the triangle formed by them. The theoretical values are in good agreement with those obtained by earlier workers from computer simulations. The present method makes it easier to optimize the number and the actual wavelengths to be employed in the multiwavelength method. The maximum benefits of this method are expected in experiments employing synchrotron radiation or neutrons.

Structural Crystallography and Crystal Chemistry

Abstract is not available.

Scanning electron microscopy studies of wear in LM13 and LM13-graphite particulate composite

Examination of the structure of worn surfaces has shown that the wear of LM13 and LM13-graphite particulate composite is controlled by the nature and extent of subsurface deformation. The addition of graphite influences the wear characteristics by affecting the plastically deformed zone. The possible mechanisms of wear are discussed.

The structures of ethyl 1,2,2-tricyano-3,3-dimethylcyclopropane-1-carboxylate and ethyl 2',3,3'-tricyanocyclohexanespirocyclopropane-2'-carboxylate

The crystal and molecular structures of C ,,H,IN302 (I) and C14HIsN302 (II) have been determined by direct methods using three-dimensional X-ray diffractometer data. Crystals of (I) are orthorhombic, space group Pna21, with a = 14.662(6), b = 10.492(5), c = 7.375 (3)A, Z = 4, V = 1134.5 A 3, D O = 1.25 (by flotation), D e = 1.269 Mgm -a, g(MoKa) = 0.085 mm -1. Crystals of (II) are monoclinic, space group P21/a, with a = 7.886 (5), b = 22.011 (8), c = 8.100 (3) A, fl = 103.12 (5) °, Z = 4, V = 1369.2 A 3, D O = 1.23 (by flotation), D e = 1.255 Mg m -3, g(Mo Kct) = 0.080 mm -1. Least-squares full-matrix refinement based on 782 (I) and 1400 independent reflections (II) converged at R = 0.040 (I) and 0.042 (II). The effect of electron-withdrawing substituents on the geometry of the cyclopropane ring is discussed.

Observability of conduction electron spin resonance (CESR) in superconductors

The condition for the observability of CESR in superconducting thin films is analysed taking into account the finiteness of the flux penetration depth. We have explicitly evaluated the path-dependent phase mixing factor occuring in the expression for power absorption. The calculated line width turns out to be of the order of, or larger than, the nominal resonance frequency for the experimentally realisable choice of parameters.

Structural Crystallography and Crystal Chemistry

CaH406P-.K +, M r = 206.10, is orthorhombic, space group Pbca (from systematic absences), a = 14.538(4), b = 13.364(5), c = 6.880 (6)A, U = 1383.9 A 3, D x = 2.07 Mg m -a, Z = 8, ~.(Mo Ka) = 0.7107/~, p(MO Ka) = 1.015 mm -1. The final R value is 0.042 for a total of 1397 reflections. The high energy P-O(13) and the enolic C(1)-O(13) bonds are 1.612 and 1.374 A respectively. The enolpyruvate moiety is essentially planar. The orientation of the phosphate with respect to the pyruvate group in PEP.K is distinctly different from that in the PEP-cyclohexylammonium salt, the torsion angle C (2)-C (1)-O(13)- P being -209.1 in the former and -90 ° in the latter. The K + ion binds simultaneously to both the phosphate and carboxyl ends of the same PEP molecule. The ester O(13) is also a binding site for the cation. The K + ion is coplanar with the pyruvate moiety and binds to 0(22) and O(13) almost along their lone-pair directions. The carbonyl 0(22) prefers to bind to the K + ion rather than take part in the formation of hydrogen bonds usually observed in carboxylic acid structures.

Electron paramagnetic resonance study of vanadyl ion in K2Zn(SO4)2·6H2O and K2Mg(SO4)2·6H2O

EPR study of the vanadyl ion has been carried out in its paramagnetically dilute form in K2Zn(SO4)2·6H2O and K2Mg(SO4)2·6H2O at room temperature at X-band. The vanadyl ion enters the divalent metal site and preferentially orients itself in the direction of the water molecules forming the octahedron and forms the vanadyl sulfate pentahydrate complex. The g and A tensorscorresponding to the two populous V-O orientations have been analyzed to obtain the principal values and their direction cosines with respect to the crystallographics axes. It is found that the g and A tensor have the same principal frames of reference within the limits of eperimental error. A correlation between the metal-water distance and the populations of the different V-O orientations is observed.

Selectivity in the Interaction of Electron Donor and Acceptor Molecules with Graphene and Single-Walled Carbon Nanotubes

Interaction of electron donor and acceptor molecules with graphene samples prepared by different methods as well as with single-walled carbon nanotubes (SWNTs) has been investigated by isothermal titration calorimetry (ITC). The ITC interaction energies of the graphene samples and SWNTs with electron acceptor molecules are higher than those with electron donor molecules. Thus, tetracyanoethylene (TCNE) shows the highest interaction energy with both graphene and SWNTs. The interaction energy with acceptor molecules varies with the electron affinity as well as with the charge-transfer transition energy for different aromatics. Metallic SWNTs interact reversibly with electron acceptor molecules, resulting in the opening of a gap.

A probabilistic approach to the problem of electron localization in disordered systems and sharpness of the mobility edge

By applying the theory of the asymptotic distribution of extremes and a certain stability criterion to the question of the domain of convergence in the probability sense, of the renormalized perturbation expansion (RPE) for the site self-energy in a cellularly disordered system, an expression has been obtained in closed form for the probability of nonconvergence of the RPE on the real-energy axis. Hence, the intrinsic mobility mu (E) as a function of the carrier energy E is deduced to be given by mu (E)= mu 0exp(-exp( mod E mod -Ec) Delta ), where Ec is a nominal 'mobility edge' and Delta is the width of the random site-energy distribution. Thus mobility falls off sharply but continuously for mod E mod >Ec, in contradistinction with the notion of an abrupt 'mobility edge' proposed by Cohen et al. and Mott. Also, the calculated electrical conductivity shows a temperature dependence in qualitative agreement with experiments on disordered semiconductors.

Electron Spectroscopic Studies of Oxygen and Carbon Dioxide Adsorbed on Metal Surfaces

Adsorption of oxygen on Ni, Cu, Pd, Ag, and Au surfaces has been investigated by employing UV and X-ray photoelectron spectrscopy as well as electron energy loss spectroscopy (EELS). Molecularly chemisorbed (singlet) oxygen is found on Ni, Cu, Ag, and Au surfaces showing features such as stabilization of the rB* orbital, destabilization of the .nu orbital, higher O(1s) binding energy than the atomic species, and a band 2-3 eV below the Fermi level due to metal d-O(2p)u* interaction. 0-0 and metal-oxygen stretching frequencies have been observed in EELS. Physical adsorption of O2 is found to occur on Pd and Ni surfaces, only at high exposures in the latter case. Physical adsorption and multilayer condensation of CO, on metal surfaces are distinguished by characteristic relaxation shifts in UPS as well as O(1s) binding energies. Adsorption of CO on a Ni surface covered with presorbed atomic oxygen gives rise to C02.

An electron spectroscopic study of the surface oxidation of glassy and crystalline Cu-Zr alloys

Surface oxidation of three metglasses in the Cu-Zr system has been investigated by employing X-ray photoelectron spectroscopy and Auger electron spectroscopy with a view to comparing their oxidation behaviour with that of the corresponding crystalline states of the alloys. Surface oxidation of pure Zr metal has also been examined in detail using these techniques. Sub-oxides of Zr are formed during the initial stages of oxidation of Zr (at oxygen exposures <10L), while at higher exposures, ZrO2 is formed together with the highest possible sub-oxide which the authors designate as 'ZrO'. The relative proportion of 'ZrO' goes through a maximum in the range 25-50 L. Both the glassy and the crystalline states of the Cu-Zr alloys exhibit preferential oxidation of Zr. The glassy alloys exhibit a higher rate of oxidation at intermediate exposures compared with the crystalline states of the alloys; the extent of oxidation at higher oxygen exposures is, however, higher for crystalline alloys. Interatomic Auger transitions have been found in the Zr+O2 system as well as in Cu-Zr alloys.

Electron spin resonance study of copper(II) doped ferroelectric ammonium sulphate

Single crystal electron spin resonance studies of Cu2+ doped ferroelectric ammonium sulphate ((NH4)2SO4, Tc = 223 K) are reported at 300 and 77 K. The Cu2+ ion is found to enter the lattice interstitially with a trigonal bipyramidal coordination. Proton superhyperfine interaction is found for magnetic field directions close to the a-axis. Changes are observed in the 77 K recordings indicating a distortion of the trigonal bipyramid consistent with crystal structure data. An increase of the proton superhyperfine constant in the ferroelectric phase is indicative of stronger hydrogen bonding. The Cu2+ ion doped as an impurity in a trigonal bipyramid environment in a diamagnetic host lattice is reported for the first time.

A high gain aluminium electron multiplier

A twenty stage electron multiplier using aluminium as dynode material is described. When operated in DC mode, very stable gains approaching 106 were obtained with input currents of the order of 10-12 A, even after repeated exposures to the atmospheres.

Dielectric and Electron Spin Resonance Spectroscopic Studies of Glassy Crystalline States of Organic Compounds

Dielectric studies of the glassy crystalline states of cyclohexanol, cyclohexanone, and camphor obtained by upercooling the plastic crystalline phase demonstrate the presence of characteristic a- and p-relaxations. The parameters of the a-relaxation fit the Vogel-Tammann-Fulcher (VTF) equation. ESR spin-probe studies of the glassy crystalline phase of cyclohexanol show that there is a marked decrease in the correlation time above the glasslike transition temperature. The present studies suggest the similarity between glassy crystals having long-range orientational disorder and glasses which are known to betra nslationally disordered.