Angle-resolved ultraviolet photoemission study of first stage alkali-metal graphite intercalation compounds

The electronic band structure of the first stage alkali-metal graphite intercalation compounds (C₈K, C₈Rb and C₈Cs) was determined by angle-resolved ultraviolet photoelectron spectroscopy. The dispersive feature of the ^* bands at point in the Brillouin zone was clearly observed in all the compounds. The electron occupancies in the ^* band of C₈K, C₈Rb and C₈Cs were estimated to be 0.5±0.05 e (e; unit electronic charge), 0.45±0.05 e and 0.4±0.05 e, respectively. This strongly suggests that another half of the unit electronic charge is accommodated in the three-dimensional band at point, which forms a spherical Fermi surface at the center of the Brillouin zone. The character of the three-dimensional band at point was also discussed.He died on 27th of September, 1986     

Theory of ring formation in a reversible system: general solutions

The enumeration theory is extended in this work into a more general theory, taking back-reactions into consideration. The solutions may faithfully reproduce real processes from arbitrary starting points to a steady-state. Therefore, the presented theory includes the equilibrium theory by Jacobson-Stockmayer, the numerical solution by Gordon-Temple, and the irreversible theory by the present authors. The solutions are described first in general forms of transition probabilities {P}, and then explicitly with the aid of rate equations; simple proofs are given. The presented theory was applied to an experimental data: the distribution of cyclic species in poly(ethylene terephthalate). We shall show that agreement between theory and experiment is nearly perfect.AB model N ₀ Total number of units - V System volume - C ₀=N ₀/N _A ·V Initial concentration (N _A : Avogadro's number) - L _x AB type chain x-mer; (AB)_x - N _x Number of AB type x-mers - R _x Ring x-mer - N _Rx Number of ring x-mers - E Small molecule eliminated by bond-formation - N _E Number of small molecules eliminated by bond-formation - h _k Number of reacted functional units (f.u.) in statek - _k Number of reacted functional units (f.u.) in chains in statek - _k Total number of units in chains in statek - D=h _k /N ₀ Extent of reaction in statek - D ^*= _k / _k Extent of reaction in chains in statek - k _L Chain-propagation rate constant - k _Rx Cyclization rate constant of chain x-mers - k _B Bond breakage rate constant of chains - k _B,Rx Bond breakage rate constant of cyclic x-mers - <k _Rx > _k Mean cyclization rate constant in statek - g(x)=k _B,Rx /k _B Ring-opening factor of cyclic x-mers - P _Lx,k Probability that a chain x-mer will be formed in statek - {P} Set of transition probabilities per single jump in forward direction or reverse direction (see the text on individual transition probabilities) AB model M _A Total AA monomer unit number - M _B Total BB monomer unit number - M ₀=M _A +M _B Total particle number - _A,i =2M _A –h _i Unreacted A functional unit (f.u.) number in statei - _B,i =2M _B –h _i Unreacted B f.u. number in statei - _Ax Unreacted A f.u. number on x-mers - h _i Number of reacted A (or B) f.u. in statei - _i Number of reacted A (or B) f.u. in chains in statei - _A,i =2M _A –h _i + _i A f.u. number in chains in statei - _B,i =2M _B –h _i + _i B f.u. number in chains in statei - _i =2(M ₀–h _i + _i ) Total f.u. number in chains in statei - D=h _i /M ₀ Extent of reaction in statei - D _A ^* = _i / _A,i Extent of reaction of A f.u. in chains in statei - D _B ^* = _i / _B,i Extent of reaction of B f.u. in chains in statei - D ^*=2 _i / _i Extent of reaction in chains in statei - L _x (AA-BB)_x-1-AA type chain x-mer;x=1,2,3,... - L _x BB-(AA-BB)_x type chain x-mer;x=0,1,2,... - L _x (AA-BB)_x type chain x-mer;x=1,2,3,... - N _x Number of type x-mers - N _x Number of type x-mers - N _x Number of type x-mers     

Periodic Oscillatory Motion of a Self-Propelled Motor Driven by Decomposition of H2O2 by Catalase

A self-propelled motor driven by the enzymatic reaction of catalase adsorbed onto a filter paper floating on an aqueous solution of H₂O₂ was used to study nonlinear behavior in the motor's motion. An increase in the concentration of H₂O₂ resulted in a change from no motion to irregular oscillatory motion, periodic oscillatory motion, and continuous motion. The mechanisms underlying oscillation and mode bifurcation are discussed based on experimental results on O₂ bubble formation and growth on the underside of the motor.     

Control on the Copper Valence and Properties by Oxygen Content Adjustment in the LaCuO3−ySystem (0≤y≤0.5)

The LaCuO_3−yperovskite is considered as the first member of the 01(n−1)nseries of “layered cuprates.” Highly oxidized, stoichiometric LaCuO₃is stabilized under very high oxygen pressures, and was synthesized in a cubic-anvil-type high-pressure apparatus at 5 GPa and 1400°C using excess amounts of KClO₄as an external oxidizing agent. Upon heating under ambient pressure the rhombohedral high-pressure phase loses oxygen yielding tetragonal, monoclinic, and orthorhombic forms of LaCuO_3−yas intermediate products before the final decomposition into La₂CuO₄and CuO or Cu₂O around 800°C. All three oxygen-deficient LaCuO_3−yphases could be isolated and their stability limits and corresponding oxygen contents conveniently investigated by annealing stoichiometric LaCuO₃in a thermobalance of high sensitivity in order toin situdetect the exact amount of oxygen loss. The nominal copper valence values calculated from the oxygen contents are compared and discussed with XPS data as well as with the results evaluated from magnetic susceptibility measurements.     

Cyclotron resonance in lead —I: Tipping effect of magnetic field

The cyclotron resonances in lead in field tipped geometry have been observed for large tipping angles up to 40° from the sample surfaces of the (111) and (100) planes. In addition to the resonance of the orbit ζ on a cylindrical arm of the electron Fermi surface, two new series of resonances, ζ^A and ζ^B have been found, of which the clotron masses are very close to that of ζ but which differ slightly in tipping angle dependence. The mass of ζ^A is dependent on microwave frequency, so that ζ^A is attributed to the Doppler-shifted cyclotron resonance of a non-stationary orbit near, ζ, whose location is discussed in relation to the Fermi surface model of Van Dyke. In field geometry normal to the (100) surface, two series of resonances have been observed, which are characterized as the extinction of even numbered harmonic resonances. This effect arises from the skipping orbit which has a trajectory topologically similar to a baseball seam in real space. One of these series is attributed to the orbit v around the junction of four electron arms.     

Concentration dependence of excluded volume effects

The concentration dependence of the excluded volume effects in polymer solutions is investigated. Through thermodynamic arguments for the interpenetration of polymer segments and the free energy change, we show that the disappearance of the excluded volume effects should occur at medium concentration. The result is in accord with the recent experimental observations.     

Dynamical symmetry breaking due to vacuum misalignment

We show that under a certain assumption systems with second-class constraints can be regarded as gauge-fixed systems with first-class constraints. The massive Yang-Mills theory, a point particle on a sphere and theO(N) symmetric non-linear σ-model are considered as concrete examples.     

Release and transfer of polystyrene dewetting pattern by hydration force

We studied the release and transfer of polystyrene (PS) microdots on mica. The PS dots were released from the mica in water. The release was affected by the density of K(+) ions on the mica surface, which was controlled by pretreatment with K(2)CO(3) solutions. The release of PS dots became dominant at the concentrations above [K(+)]crit = 1 x 10(-4) M in the K(2)CO(3) solution. In this concentration region, repulsive forces appeared as a result of the hydration of K(+) ions on the mica (J. Colloid Interface Sci. 1981, 83, 531). This result suggests that the repulsive hydration force causes the release of the PS dots. Followed by the release process, we successfully demonstrated the transfer of the array of PS dots from the mica to another substrate.