Anionic Sublattices in Halide Solid Electrolytes: A Case Study with the High-Pressure Phase of Li3ScCl6

The Li₃MX₆ compounds (M=Sc, Y, In; X=Cl, Br) are known as promising ionic conductors due to their compatibility with typical metal oxide cathode materials. In this study, we have successfully synthesized γ-Li₃ScCl₆ using high pressure for the first time in this family. Structural analysis revealed that the high-pressure polymorph crystallizes in the polar and chiral space group P6₃mc with hexagonal close-packing (hcp) of anions, unlike the ambient-pressure α-Li₃ScCl₆ and its spinel analog with cubic closed packing (ccp) of anions. Investigation of the known Li₃MX₆ family further revealed that the cation/anion radius ratio, r_M/r_X, is the factor that determines which anion sublattice is formed and that in γ-Li₃ScCl₆, the difference in compressibility between Sc and Cl exceeds the ccp r_M/r_X threshold under pressure, enabling the ccp-to-hcp conversion. Electrochemical tests of γ-Li₃ScCl₆ demonstrate improved electrochemical reduction stability. These findings open up new avenues and design principles for lithium solid electrolytes, enabling routes for materials exploration and tuning electrochemical stability without compositional changes or the use of coatings.     

Quantification of local oxygen defects around Yttrium ions for yttria-doped ceria–zirconia ternary system

Local coordination structure around Yttrium ions in CeO₂–Y₂O₃ binary and [(CeO₂)_x(ZrO₂)_1?x]_0.8(YO_1.5)_0.2 (x = 0.0 ~ 1.0) ternary system has been investigated by ⁸⁹Y MAS-NMR. NMR spectra are found to be consisted of multiple peaks that can be assigned to 6-, 7- and 8-oxygen coordinated Yttrium ions. Compositional dependence of the spectrum was observed and compared with the previous results for ZrO₂–Y₂O₃ binary system. The present investigation suggested the degree of localization of the oxygen vacancy around the cation is in the order of Zr⁴⁺ > Y³⁺ > Ce⁴⁺. The degree of the oxygen vacancy preference for each cation was quantitatively determined for CeO₂–ZrO₂–Y₂O₃ ternary system the first time.     

On extensions of some Flugede–Putnam type theorems involving (p,k)‐quasihyponormal,spectral, and dominant operators

A Hilbert space operator S is called (p, k)‐quasihyponormal if S *^k ((S *S)^p – (SS *)^p )S^k ≥ 0 for an integer k ≥ 1 and 0 < p ≤ 1. In the present note, we consider (p, k)‐quasihyponormal operator S ∈ B (H) such that SX = XT for some X ∈ B (K,H) and prove the Fuglede–Putnam type theorems when the adjoint of T ∈ B (K) is either (p, k)‐quasihyponormal or dominant or a spectral operator (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Classifying homeomorphism groups of infinite graphs

In this paper, we classify topologically the homeomorphism groups H(Γ) of infinite graphs Γ with respect to the compact-open and the Whitney topologies.     

Well-posedness and weak rotation limit for the Ostrovsky equation

We consider the Cauchy problem of the Ostrovsky equation. We first prove the time local well-posedness in the anisotropic Sobolev space Hs,a with s>−a/2−3/4 and 0?a?−1 by the Fourier restriction norm method. This result include the time local well-posedness in Hs with s>−3/4 for both positive and negative dissipation, namely for both βγ>0 and βγ<0. We next consider the weak rotation limit. We prove that the solution of the Ostrovsky equation converges to the solution of the KdV equation when the rotation parameter γ goes to 0 and the initial data of the KdV equation is in L². To show this result, we prove a bilinear estimate which is uniform with respect to γ.     

Second-harmonic spectroscopy of surface immobilized gold nanospheres above a gold surface supported by self-assembled monolayers

We have investigated linear and nonlinear optical properties of surface immobilized gold nanospheres (SIGNs) above a gold surface with a gap distance of a few nanometers. The nanogap was supported by amine or merocyanine terminated self-assembled monolayers (SAMs) of alkanethiolates. A large second-harmonic generation (SHG) was observed from the SIGN systems at localized surface plasmon resonance condition. The maximum enhancement factor of SHG intensity was found to be 3 x 10(5) for the SIGN system of nanospheres 100 nm in diameter with a gap distance of 0.8 nm. The corresponding susceptibility was estimated to be chi((2))=750 pmV (1.8 x 10(-6) esu). In the SIGN system supported with the merocyanine terminated SAMs, the SHG response was also resonant to the merocyanine in the nanogap. It was found that the SHG response of the SIGN systems is strongly frequency dependent. This leads us to conclude that the large chi((2)) is caused by enhanced electric fields at the localized surface plasmon resonance condition and is not due to an increase of the surface susceptibility following from the presence of the gold nanospheres. The observed SHG was consistent with the theoretical calculations involving Fresnel correction factors, based on the quasistatic approximation.     

Synthetic studies on chartelline C: stereoselective construction of the core skeleton

What a core-ker! The title synthesis was achieved using a route featuring an intramolecular Mitsunobu reaction of a nosyl amide, stereoselective construction of the β-lactam, and formation of an enamide moiety by selenoxide elimination. The stereochemistry of the alkylation for the formation of the β-lactam was controlled by a secondary hydroxy group on the ten-membered ring. SEM=2-(trimethylsilyl)ethoxymethyl; TBS=tert-butyldimethylsilyl.     

Photo-impulsive reactions in the electronic ground state without electronic excitation: non-photo, non-thermal chemical reactions

Allyl phenyl ether has an absorption band in the ultraviolet region (λ < 400 nm); therefore, irradiation with few-optical-cycle ultraviolet pulses (λ = 360-440 nm) causes a transition to the ultraviolet band, which leads to an electronic state and a photo-Claisen rearrangement (radical reaction) in the electronic excited state. However, the reaction scheme of allyl phenyl ether under irradiation with few-optical-cycle visible pulses (λ = 525-725 nm) was determined to be same as that of the thermal Claisen rearrangement ([3,3]-sigmatropic rearrangement), which is symmetry-allowed in the electronic ground state. Photo-excitation with few-optical cycle visible pulses below the absorption band induces a photo-impulsive reaction in the electronic ground state without electronic excitation, of which the trigger scheme is different from that of photoreaction or thermal-reaction. The photo-impulsive reaction in the electronic ground state is highly possible as a novel reaction scheme.     

A narrow process window for the preparation of polytypes of microcrystalline silicon carbide thin films by hot-wire CVD method

Effects of deposition conditions on the structure of microcrystalline silicon carbide (μc-SiC) films prepared by hot-wire chemical vapor deposition (hot-wire CVD) method have been investigated. It is found from X-ray diffraction patterns of the film that a diffraction peak from crystallites from hexagonal polytypes of SiC is observed in addition to those of 3 C-SiC crystallites. This result is obtained in the film under a narrow deposition conditions of SiH₃CH₃ gas pressure of 8 Pa, the H₂ gas pressure of 80–300 Pa and the total gas pressure of 40–300 Pa under fixed substrate and filament temperatures employed in this study. Furthermore, the grain size of hexagonal crystallites (about 20 nm) on c-Si substrates becomes larger than that of 3 C-SiC crystallites (about 10 nm) for the films deposited under the total gas pressure of 36–88 Pa. The fact that microcrystalline hexagonal SiC can be deposited under limited deposition conditions could be interpreted in the context of a result for c-SiC polytypes prepared by thermal CVD method.