Analysis of Thermodynamic Properties for Rare Earth Complexes in Ionic Liquids by Raman Spectroscopy and DFT Calculation

The coordination states of the divalent and trivalent rare earth complexes in ionic liquid, triethyl-pentyl-phosphonium bis(trifluoromethyl-sulfonyl) amide [P2225][TFSA] were investigated by Raman spectroscopy and DFT calculation. The concentration dependences of the deconvoluted Raman spectra were investigated for 0.23-0.45 mol kg-1 RE(III), RE=Nd and Dy, and the mixed sample of RE(II)/RE(III)=1/3 at the molar ratio in [P2225][TFSA]. According to the conventional analysis, the solvation number; n of rare earth complexes in [P2225][TFSA] were determined to be n=4.06 for Nd(II), 5.01 for Nd(III), 4.12 for Dy(II) and 5.00 for Dy(III). Thermodynamic properties such as ΔisoG, ΔisoH and ΔisoS for the isomerism of [TFSA]- from trans- to cis-isomer in bulk and the first solvation sphere of the centered [RE3+] cation in [P2225][TFSA] were evaluated from the temperature dependence in the range of 298-398K. ΔisoG(bulk), ΔisoH(bulk) and TΔisoS(bulk) at 298 K were -1.06, 6.86, and 7.92 kJ mol-1, respectively. The trans-[TFSA]-was dominant in the enthalpy due to the positive value of ΔisoH(bulk) and TΔisoS(bulk) was slightly larger than ΔisoH(bulk), so that cis-[TFSA]- was revealed to be an entropy-controlled in [P2225][TFSA]. On the other hand, in the first solvation sphere of [RE3+] cation, ΔisoH (Nd)(-47.39 kJ mol-1) increased to the negative value remarkably and implied that the cis-[TFSA]- isomers were stabilized for enthalpy. ΔisoH(Nd) contributed to the remarkable decrease in the ΔisoG(Nd) and this result clearly indicated that the cis-[TFSA]- bound to Nd3+ cation was preferred and the coordination state of [Dy(III)(cis-TFSA)5]2- was stable in [P2225][TFSA] The optimized geometries and the bonding energies of [RE(II)(cis-TFSA)4]2- and [RE(III)(cis-TFSA)5]2- clusters were also investigated from DFT calculation with ADF package. The bonding energy; ΔEb was calculated from ΔEb= Etot(cluster) - Etot(RE2,3+) - nEtot([TFSA]-). ΔEb([Nd(II)(cis-TFSA)4]2-), ΔEb([Nd(III)(cis-TFSA)5]2-), ΔEb([Dy(II)(cis-TFSA)4]2-) and ΔEb([Dy(III)(cis-TFSA)5]2-) were -2241.6, -4362.3, -2135.4 and -4284.2 kJmol-1, respectively. This result was revealed that [RE(III)(cis-TFSA)5]2-cluster formed stronger coordination bonds than [Dy(II)(cis-TFSA)4]2- cluster. The average atomic charges and the bond distances of these clusters were consistent with the thermodynamic properties

Statistical Properties of Gamma-Ray Burst Polarization

The emission mechanism and the origin and structure of magnetic fields in gamma-ray burst (GRB) jets are among the most important open questions concerning the nature of the central engine of GRBs. In spite of extensive observational efforts, these questions remain to be answered and are difficult or even impossible to infer with the spectral and lightcurve information currently collected. Polarization measurements will lead to unambiguous answers to several of these questions. Recent developments in X-ray and gamma-ray polarimetry techniques have demonstrated a significant increase in sensitivity enabling several new mission concepts, e.g. POET (Polarimeters for Energetic Transients), providing wide field of view and broadband polarimetry measurements. If launched, missions of this kind would finally provide definitive measurements of GRB polarizations. We perform Monte Carlo simulations to derive the distribution of GRB polarizations in three emission models; the synchrotron model with a globally ordered magnetic field (SO model), the synchrotron model with a locally random magnetic field (SR model), and the Compton drag model (CD model). The results show that POET, or other polarimeters with similar capabilities, can constrain the GRB emission models by using the statistical properties of GRB polarizations. In particular, the ratio of the number of GRBs for which the polarization degrees can be measured to the number of GRBs that are detected (N_m/N_d) and the distributions of the polarization degrees (Pi) can be used as the criteria. If N_m/N_d > 30% and Pi is clustered between 0.2 and 0.7, the SO model will be favored. If instead N_m/N_d < 15%, then the SR or CD model will be favored. If several events with Pi > 0.8 are observed, then the CD model will be favored.Comment: Replaced with accepted version in ApJ. A few minor changes done. References adde

A Report on Overseas Teaching Practicum by Graduate Students in Elementary/Secondary Schools in the United States（Ⅹ）

This short paper reports on the 10th overseas teaching practicum in the United States by 8 graduate students of Hiroshima University， Japan， partly organized by Hiroshima University Global Partnership School Center (GPSC). This year marks the 10-year anniversary of this project since its start. This year’s participants were students of Graduate School of Education and Graduate School for International Development and Cooperation (IDEC). They observed and conducted lessons in English in four local public schools in North Carolina. This project had the following three aims: 1) to self-develop practical instructional competence by teaching pupils with different cultural backgrounds; 2) to enhance the abilities in developing teaching materials through hands-on teaching experiences in English; and 3) to acquire the abilities to design， implement and evaluate programs for promoting global partnership. Like previous years， their teachings were very positively covered by the local newspapers and websites. Later， the project was followed by cross-cultural field study visits to NC State Capitol， Raleigh and the U.S. Capitol， Washington， D.C. It is hoped that this intensive experience will raise the prospective teachers’ global awareness and confidence in teaching

A Report on Overseas Teaching Practicum by Graduate Students in Elementary/Secondary Schools in the United States (Ⅶ)

The present reports is on the 7th overseas teaching practicum in the United States by 15 graduate students of Hiroshima University, Japan, partly organized by Hiroshima University Global Partnership School Center since 2007. The group was comprised of 13 elementary school and 2 secondary school education major graduate students. They planned and conducted lessons in English in three local public schools in North Carolina. The expected outcomes of this project were: 1) to self-develop practical instructional competence by teaching pupils with diverse backgrounds in the U.S.; 2) to enhance the abilities in developing teaching materials through hands-on teaching experiences in English; and 3) to acquire the abilities to design, implement and evaluate programs for promoting global partnership. In addition, the teaching experience was followed by cross-cultural study visits to Raleigh, NC and Washington, D.C. It helped to boost our group motivation that the local media, newspaper and TV, and the city Board of Education covered our visit. It is hoped that this project will enhance the students’ teaching competence in designing quality materials/lessons and classroom communication skills in English