Controllable Electronic Structures and Photoinduced Processes of Bay‐Linked Perylenediimide Dimers and a Ferrocene‐Linked Triad

A series of perylene‐3,4,9,10‐bis(dicarboximide) (PDI) dimers linked through the bay regions was systematically synthesized to examine the electronic structures and photophysical properties in dependence on the distance and orientation between the two PDI units. The spectroscopic and electrochemical measurements suggested that the coupling value of a directly linked PDI dimer (PDI)₂ is much larger than those of para‐ and meta‐phenylene‐bridged PDI dimers p‐(PDI)₂ and m‐(PDI)₂. The width of Davydov splitting was quantitatively evaluated to compare the coupling values between the two PDI units in these dimers by absorption spectroscopy in frozen 2‐methyl‐THF. Excimer formation of PDI dimers induced the strong fluorescence quenching and large red‐shifts. Femtosecond transient absorption revealed a broad absorption derived from an excimer in the range from about 600 nm to the near‐IR region. The rate constants of formation and decay of the excimer are strongly dependent on the coupling values. Time‐resolved measurements on ferrocene‐linked p‐(PDI)₂ revealed a competition between the photoinduced processes of electron transfer and excimer formation in PhCN, which is in sharp contrast with the sole electron‐transfer process in toluene.     

Synthesis, crystal structure, and structural conversion of Ni molybdate hydrate NiMoO4·nH2O

The synthesis and crystal structure of NiMoO₄·nH₂O were investigated. The hydrate crystallized in the triclinic system with space group P−1, Z=4 with unit cell parameters of a=6.7791(2) Å, b=6.8900(2) Å, c=9.2486(2) Å, α=76.681(2)°, β=83.960(2)°, γ=74.218(2)°. Its ideal chemical composition was NiMoO₄·3/4H₂O rather than NiMoO₄·1H₂O. Under hydrothermal conditions the hydrate turned directly into α-NiMoO₄ above 483 K, giving nanorods thinner than the crystallites of the mother hydrate. On the other hand, it turned into Anderson type of polyoxomolybdate via a solid-solution process in a molybdate solution at room temperature.     

Mermin-ho vortex in ferromagnetic spinor Bose-Einstein condensates

The Mermin-Ho and Anderson-Toulouse coreless vortices are demonstrated to be thermodynamically stable in ferromagnetic F = 1 spinor Bose-Einstein condensates under rotation. We have carried out extensive calculations of the Gross-Pitaevskii equations by assuming uniform density along the z axis and comparing the energies of other competing non-axis-symmetric or singular vortices. The phase diagram is thereby established in a plane of the rotation drive vs the total magnetization. Their stability is also checked by calculating collective modes based on the Bogoliubov equations.     

Characterization of diene polymers. I. Infrared and NMR studies: Nonadditive behavior of characteristic infrared bands

Extinction coefficients of the characteristic infrared bands due to isomeric structural units were measured for polybutadiene and polyisoprene in CS₂ or CCl₄ solutions and were compared with the isomer composition determined by NMR. The NMR signal assignments were made on the basis of the spectra of deutero derivatives of the polymers. In the case of polyisoprene, linear relations were obtained between the extinction coefficients and the isomer contents determined by NMR for the absorption bands at 1385 cm^?1 (characteristic of trans-1,4 units), 1376 cm^?1 (cis-1,4 units), and 889 cm^?1 (3,4 units). However, for the absorption bands at 840 cm^?1 (characteristic of cis-1,4 and trans-1,4 units), isomerized polyisoprenes did not give such a linear relationship. In polybutadiene, the extinction coefficient for the atactic 1,2 units was found to be lower than that of the syndiotactic 1,2 unit. These experimental facts lead to the conclusion that additivity of the extinction coefficients does not always hold for diene polymers. The deviation from the linear relation may be associated with regular sequences of one isomeric conformation in the chain.     

Measurement of Cu K-shell and Ag L-shell ionization cross sections by low-energy positron impact

Inner shell ionization cross sections by low-energy positron impact have been measured. Development of an x-ray detector with thin Si(Li) crystals has enabled the first measurements of the absolute cross sections for the positron impacts in the energy range below 30 keV. Threshold behavior of the measured cross sections for the Cu K shell and Ag L shell are compared with the theoretical results of Gryzinski and Kowalski [Phys. Lett. A 183, 196 (1993)]] and Khare and Wadehra [Can. J. Phys. 74, 376 (1996)]]. Good agreement has been found for the Cu K shell, while the experimental values for the Ag L shell were found to be smaller than the corresponding theoretical results.     

Modulational instability and parametric amplification induced by loss dispersion in optical fibers

We show that modulational instability may arise even in the normal group-velocity dispersion regime of an optical fiber when the fiber loss (gain) varies depending on the wavelength. A simple analytical expression for the instability gain is obtained, which reveals that the odd-order terms of the loss dispersion are responsible for this phenomenon. The instability gain is measured experimentally in an optical-parametric-amplification configuration. Large parametric gain is induced in a non-phase-matched regime as we apply narrow band loss at the idler wavelength.     

Memory effect in the chain-collapse process in a dilute polymer solution

The effect of temperature perturbation on a single-chain-collapse process was studied for poly(methyl methacrylate) with the molecular weight M(w)=1.05 x 10(7) in the mixed solvent of tert-butyl alcohol+water (2.5 vol %). In the chain-collapse process after a quench from the theta; temperature to a temperature T(1), the temperature was changed from T(1) to T(2) at the time t(1) after the quench and returned to T(1) at the time t(1)+t(2). In the three stages at T(1), T(2), and T(1), measurements of the mean-square radius of gyration of polymer chains were carried out by static light scattering and the chain-collapse process was represented by the expansion factor as a function of time. An effect of chain aggregation on the measurements was negligibly small because of the very slow phase separation. For the negative temperature perturbation (T(1)>T(2)), the chain-collapse processes observed in the first and third stages were connected smoothly and agreed with the collapse process due to a single-stage quench to T(1). A memory of the chain collapse in the first stage at T(1) was found to persist into the third stage at the same temperature T(1) without being affected by the temperature perturbation of T(2) during t(2). The memory effect was observed irrespective of the time period of t(2). The positive temperature perturbation (T(1)相似文献