Microscopic theory of multipole ordering in NpO2

In order to examine the mysterious ordered phase of NpO2 from a microscopic viewpoint, we investigate an f-electron model on an fcc lattice constructed based on a j-j coupling scheme. First, an effective model with multipole interactions is derived in the strong-coupling limit. Numerical analysis of the model clearly indicates that the interactions for \Gamma_{4u} and \Gamma_{5u} moments are relevant to the ground state. Then, by applying mean-field theory to the simplified model including only such interactions, we conclude that longitudinal triple-q \Gamma_{5u} octupole order is realized in NpO2 through the combined effects of multipole interactions and anisotropy of the \Gamma_{5u} moment.Comment: 5 pages, 2 figure

DFT/TD-DFT molecular design of porphyrin analogues for use in dye-sensitized solar cells

Density functional theory (DFT) and time-dependent DFT calculations have been employed to model Zn meso-tetraphenylporphyrin (ZnTPP) complexes having different b-substituents, in order to design an efficient sensitizer for dye-sensitized solar cells. To calculate the excited states of the porphyrin analogues, at least the TD-B3LYP/6-31G* level of theory is needed to replicate the experimental absorption spectra. Solvation results were found to be invariant with respect to the type of model used (PCM vs. C-PCM). Most of the electronic transitions based on Gouterman’s four-orbital model of ZnTPP-A and ZnTPP-B are p - p* transitions, so that cell efficiency can be enhanced by increasing the p-conjugation and electron-withdrawing capability of the bsubstituent. This proposition was tested by inserting thiophene into the b-substituent of ZnTPP-A to form a new analogue, ZnTPP-C. Compared with ZnTPP-A and ZnTPP-B, ZnTPP-C has a smaller band gap, which brings LUMO closer to the conduction band of TiO2, and a red-shifted absorption spectrum with higher extinction coefficients, especially in the Q-band positio

Experimental and theoretical analysis of organic dyes having a double D-π-A configurations for dye-sensitized solar cells

Two spiro-like organic dyes linked at the thiophene bridge (KS-11 and KS-12) together with the original rod-shaped D-π-A configuration (C1) were designed, synthesized, and characterized based on their electronic structure, and determine the photophysical and photovoltaic properties for its application in dye-sensitized solar cells. Compared to C1, the double D-π-A spiro-like configuration, which consists of two separated light-harvesting moieties, was found to be beneficial to photocurrent generation provided that they are separated properly to prevent intramolecular exciton annihilation. This was observed when KS-11, which is linked at the β-position of the thiophene moiety of D-π-A, was compared with KS-12, where the two D-π-A are linked with an additional thiophene using a α-β linkage. The results show that KS-12 produced a 20% and 17% increase in photovoltaic efficiency under simulated AM 1.5G solar irradiation compared to KS-11 and C1, respectively. This increase in photovoltaic performance is credited mostly to the reduction of recombination effects and the increase in the density of states at the semiconductor surface due to high dye loading and better charge-transfer properties

Resonant X-Ray Scattering on the M-Edge Spectra from Triple-k Structure Phase in U_{0.75}Np_{0.25}O_{2} and UO_{2}

We derive an expression for the scattering amplitude of resonant x-ray scattering under the assumption that the Hamiltonian describing the intermediate state preserves spherical symmetry. On the basis of this expression, we demonstrate that the energy profile of the RXS spectra expected near U and Np M_4 edges from the triple-k antiferromagnetic ordering phase in UO_{2} and U_{0.75}Np_{0.25}O_{2} agree well with those from the experiments. We demonstrate that the spectra in the \sigma-\sigma' and \sigma-\pi' channels exhibit quadrupole and dipole natures, respectively.Comment: 3 pages, 3 figures, to be published in J. Phys. Soc. Jpn. Supp

Evidence for Octupole Order in Ce0.7_{0.7}La0.3_{0.3}B6_6 from Resonant X-ray Scattering

The azimuthal angle dependence observed in the resonant X-ray scattering in phase IV of Ce$_{0.7}$La$_{0.3}$B$_6$ is analyzed theoretically. It is shown that the peculiar angle dependence observed in the E2 channel is consistent with the Gamma_{5u}-type octupole order with principal axis along (111) and equivalent directions. Under the assumption that the four equivalent octupole domains are nearly equally populated in the sample, the observed angle dependences are reproduced by calculation for both sigma-sigma' and sigma-pi' polarizations. The calculation for various symmetries of order parameters excludes unambiguously other order parameters than the Gamma_{5u}-type octupole.Comment: 4 pages, 2 figures, 3 tables, in JPSJ forma

Multipole correlations in low-dimensional f-electron systems

By using a density matrix renormalization group method, we investigate the ground-state properties of a one-dimensional three-orbital Hubbard model on the basis of a j-j coupling scheme. For $B_4^0 \ne 0$, where $B_4^0$ is a parameter to control cubic crystalline electric field effect, one orbital is itinerant, while other two are localized. Due to the competition between itinerant and localized natures, we obtain orbital ordering pattern which is sensitive to $B_4^0$, leading to a characteristic change of $\Gamma_{3g}$ quadrupole state into an incommensurate structure. At $B_4^0 = 0$, all the three orbitals are degenerate, but we observe a peak at $q = 0$ in $\Gamma_{3g}$ quadrupole correlation, indicating a ferro-orbital state, and the peak at $q = \pi$ in $\Gamma_{4u}$ dipole correlation, suggesting an antiferromagnetic state. We also discuss the effect of $\Gamma_{4u}$ octupole on magnetic anisotropy.Comment: 4 pages, 3 figures, Proceedings of ASR-WYP-2005 (September 27-29, 2005, Tokai

Satellite holmium M-edge spectra from the magnetic phase via resonant x-ray scattering

Developing an expression of resonant x-ray scattering (RXS) amplitude which is convenient for investigating the contributions from the higher rank tensor on the basis of a localized electron picture, we analyze the RXS spectra from the magnetic phases of Ho near the $M_{4,5}$ absorption edges. At the $M_5$ edge in the uniform helical phase, the calculated spectra of the absorption coefficient, the RXS intensities at the first and second satellite spots capture the properties the experimental data possess, such as the spectral shapes and the peak positions. This demonstrates the plausibility of the adoption of the localized picture in this material and the effectiveness of the spectral shape analysis. The latter point is markedly valuable since the azimuthal angle dependence, which is one of the most useful informations RXS can provides, is lacking in the experimental conditions. Then, by focusing on the temperature dependence of the spectral shape at the second satellite spot, we expect that the spectrum is the contribution of the pure rank two profile in the uniform helical and the conical phases while that is dominated by the rank one profile in the intermediate temperature phase, so-called spin slip phase. The change of the spectral shape as a function of temperature indicates a direct evidence of the change of magnetic structures undergoing. Furthermore, we predict that the intensity, which is the same order observed at the second satellite spot, is expected at the fourth satellite spot from the conical phase in the electric dipolar transition.Comment: 24 pages, 5 figure