Study of band inversion in the PbxSn1-xTe class of topological crystalline insulators using x-ray absorption spectroscopy.

Pb(x)Sn(1-x)Te and Pb(x)Sn(1-x)Se crystals belong to the class of topological crystalline insulators where topological protection is achieved due to crystal symmetry rather than time-reversal symmetry. In this work, we make use of selection rules in the x-ray absorption process to experimentally detect band inversion along the PbTe(Se)-SnTe(Se) tie-lines. The observed significant change in the ratio of intensities of L1 and L3 transitions along the tie-line demonstrates that x-ray absorption can be a useful tool to study band inversion in topological insulators.

RISING beamline (BL28XU) for rechargeable battery analysis.

The newly installed BL28XU beamline at SPring-8 is dedicated to in situ structural and electronic analysis of rechargeable batteries. It supports the time range (1 ms to 100 s) and spatial range (1 µm to 1 mm) needed for battery analysis. Electrochemical apparatus for battery charging and discharging are available in experimental hutches and in a preparation room. Battery analysis can be carried out efficiently and effectively using X-ray diffraction, X-ray absorption fine-structure analysis and hard X-ray photoelectron spectroscopy. Here, the design and performance of the beamline are described, and preliminary results are presented.

Quick-scanning x-ray absorption spectroscopy system with a servo-motor-driven channel-cut monochromator with a temporal resolution of 10 ms.

We have developed a quick-scanning x-ray absorption fine structure (QXAFS) system and installed it at the recently constructed synchrotron radiation beamline BL33XU at the SPring-8. Rapid acquisition of high-quality QXAFS data was realized by combining a servo-motor-driven Si channel-cut monochromator with a tapered undulator. Two tandemly aligned monochromators with channel-cut Si(111) and Si(220) crystals covered energy ranges of 4.0-28.2 keV and 6.6-46.0 keV, respectively. The system allows the users to adjust instantly the energy ranges of scans, the starting angles of oscillations, and the frequencies. The channel-cut crystals are cooled with liquid nitrogen to enable them to withstand the high heat load from the undulator radiation. Deformation of the reflecting planes is reduced by clamping each crystal with two cooling blocks. Performance tests at the Cu K-edge demonstrated sufficiently high data quality for x-ray absorption near-edge structure and extended x-ray absorption fine-structure analyses with temporal resolutions of up to 10 and 25 ms, respectively.

Distortion-triggered loss of long-range order in solids with bonding energy hierarchy.

An amorphous-to-crystal transition in phase-change materials like Ge-Sb-Te is widely used for data storage. The basic principle is to take advantage of the property contrast between the crystalline and amorphous states to encode information; amorphization is believed to be caused by melting the materials with an intense laser or electrical pulse and subsequently quenching the melt. Here, we demonstrate that distortions in the crystalline phase may trigger a collapse of long-range order, generating the amorphous phase without going through the liquid state. We further show that the principal change in optical properties occurs during the distortion of the still crystalline structure, upsetting yet another commonly held belief that attributes the change in properties to the loss of long-range order. Furthermore, our results suggest a way to lower energy consumption by condensing phase change inducing energy into shorter pulses or through the use of coherent phonon excitation.

Formation of chlorinated aromatics in model fly ashes using various copper compounds.

Various copper compounds found in fly ash are related to the formation of chlorinated aromatics. The formation potentials of chlorinated aromatics in different model fly ashes containing various copper compounds and the chemical behavior of such copper compounds were investigated. In model fly ash with copper metal, hydroxide, carbonate, or oxides, the generated amounts of chlorobenzene (CBz) and polychlorinated biphenyls (PCBs) and the average chlorination numbers were low and at the same level, respectively. The maximum generated amounts of chlorinated aromatics were observed at 300 degrees C. Although X-ray absorption near edge structure (XANES) spectra indicated that the chemical form of copper compounds changed little, they were found to promote the formation of chlorinated aromatics. Therefore, these copper compounds play the same role as CuO. On the other hand, in model fly ash with copper chloride, the generated amounts of CBz and PCBs were quite high and the average chlorination numbers was high. Dynamic changes were observed in XANES spectra, and the pre-edge peak attributed to monovalent copper compounds appeared at around 300 degrees C. A large difference was observed between these two groups in the amount of CuCl generated and the homologs of chlorinated aromatics present, indicating that CuCl played an important role in the formation of chlorinated aromatics.

Toward the ultimate limit of phase change in Ge(2)Sb(2)Te(5).

The limit to which the phase change memory material Ge(2)Sb(2)Te(5) can be scaled toward the smallest possible memory cell is investigated using structural and optical methodologies. The encapsulation material surrounding the Ge(2)Sb(2)Te(5) has an increasingly dominant effect on the material's ability to change phase, and a profound increase in the crystallization temperature is observed when the Ge(2)Sb(2)Te(5) layer is less than 6 nm thick. We have found that the increased crystallization temperature originates from compressive stress exerted from the encapsulation material. By minimizing the stress, we have maintained the bulk crystallization temperature in Ge(2)Sb(2)Te(5) films just 2 nm thick.

Chemical states of trace elements in sewage sludge incineration ash by using x-ray absorption fine structure.

In this study, the chemical states of chromium (Cr), arsenic (As), and selenium (Se) in sewage sludge incineration ash were determined by X-ray absorption fine structure (XAFS) spectroscopy. Sewage sludge incineration ash was sampled from several facilities, and XAFS measurements were carried out with a beam line BL01B1 at the SPring-8 facility. Cr K-edge X-ray absorption near-edge structure (XANES) spectra suggested that Cr compounds were predominantly speciated as Cr(III) and the fraction of Cr(VI) was very minor. Compared to the reference materials, Cr XANES spectra of the incineration ashes were similar to those of FeCr2O4, Cr(OH)3, and CaCr2O4. As K-edge XANES spectra indicated that As(V) compounds were present in incineration ashes. Because the chemical state of As in sewage sludge was As3+ in our previous study, we speculated that the chemical state of As changed into As(V) during the incineration process. According to Se K-edge XANES spectra, Se compounds were predominantly Se(IV), and a slight difference was observed in the chemical states amongst facilities using inorganic or organic coagulants in the dewatering process.

Pressure-induced site-selective disordering of Ge2Sb2Te5: a new insight into phase-change optical recording.

We demonstrate that , the material of choice in phase-change optical recording (such as DVD-RAM), can be rendered amorphous by the application of hydrostatic pressure. It is argued that this structural change is due to a very strong second-nearest-neighbor Te-Te interaction that determines the long-range order in the metastable cubic phase of and also to the presence of vacancies. This newly discovered phenomenon suggests that pressure is an important factor for the formation of the amorphous phase which opens new insight into the mechanism of phase-change optical recording.

EXAFS spectra above Pb and Pt K edges observed at low temperature.

X-ray absorption spectra near K edges of Pb (88.0keV) and Pt (78.4keV) for the foils were measured in transmission mode at SPring-8. We succeeded for the first time in observing the EXAFS oscillation of the Pb foil at 12K, although it was failed at room temperature in a previous experiment. The amplitude of the EXAFS oscillation of the Pt foil at 12K considerably increased in comparison with that at room temperature, indicating that the amplitude is very sensitive to the Debye-Waller factor at high-k values.

XANES study of charge ordering on the spin-Peierls phase transition of alpha'-NAV2O5.

alpha'-NaV2O5 transforms at Tc = 34K, and the origin of the phase transition seems to be caused by the charge order and spin-Peierls mechanism. However the experiments which reveal the existence of charge order are very little. We measured XANES of V atoms which relates to the valence of V. It was found that the valences of V atoms in NaV2O5 were V4.5+ in the high temperature phase by comparing pre-edge and XANES of NaV2O5 with that of LiV2O5 CaV2O5 and V2O5. The analysis of EXAFS also shows the environment of the V4.5+ state.

Standard transport channels of X-ray beamlines at SPring-8.

SPring-8 is constructing most of its beamlines using a combination of standardized components. The structures of the beamlines are also standardized according to the light-source characteristics. Specifications of components as well as the unified method of assembly and alignment are described.

The specific binding site of the volatile anesthetic diiodomethane to purple membrane by X-ray diffraction.

To determine the binding site of volatile anesthetics on purple membrane, diiodomethane (CH2I2) was used as a label in X-ray diffraction experiments. At less than 3 mM diiodomethane, purple membrane retains its two-dimensional crystallinity of bacteriorhodopsin, absorption spectra show only a little blue shift and the decay time of the M-intermediate becomes fast in flash photolysis experiments. These effects are similar to those of other anesthetics previously studied. The position where the anesthetic binds was identified by difference Fourier methods, and refined by model calculations. This study suggests that volatile anesthetics bind specifically to the protein-lipid interfacial region near the surface of membrane.

The hydration of Ras p21 in solution during GTP hydrolysis based on solution X-ray scattering profile.

The small-angle X-ray scattering technique was used to characterize the structure in solution of wild type ras p21 as well as the oncogenic proteins mutated at residue 12, 59, or 61. In the presence of GDP, the radius of gyration, Rg, determined for wild type ras p21 was 16.89 +/- 0.01 A, while the wild type ras p21 bound to the GTP analogue GDPNHP (5'-guanyl imido diphosphate beta-gamma-imidoguanosine 5'-triphosphate) showed an Rg value of 17.46 +/- 0.01 A, which is 3.3% larger. The result shows that ras p21 expands upon GTP binding. The Rgs of mutated proteins were 17.04 +/- 0.01, 16.98 +/- 0.01, and 17.03 +/- 0.01 A for the Gly-12 to Val, Ala-59 to Thr, and Gln-61 to Leu mutants, respectively. The scattering profiles were analyzed by simulation of hydrated ras p21, based on the crystal atomic coordinates, and it was concluded that the ras p21 molecule incorporates 20% more bulk water upon GTP binding. The increase of bulk water is especially conspicuous around the interface between switch I (residues 32-40) and switch II (residues 60-66) regions. This suggests that hydration plays an important role in the interaction with GAP.

Effects of volatile anesthetics on bacteriorhodopsin in purple membrane, Halobacterium halobium cells and reconstituted vesicles.

In this study, we have investigated effects of volatile anesthetics on absorption spectra, proton pumping activity and decay of photointermediate M of bacteriorhodopsin (bR) in differently aggregated states. Anesthetics used in this study are ether-type general anesthetics; enflurane and sevoflurane. The observed effects on bR depend not only on variety or concentration of anesthetics but also strongly on the aggregation state of bR molecules in the membrane. In purple membrane (PM), bR having maximum light absorption at 567 nm (bR567) is formed in the presence of sevoflurane or a small amount of enflurane, while a species absorbing maximally at 480 nm (bR480) is formed upon the addition of large amounts of enflurane. X-ray diffraction studies show that the former species maintains crystallinity of PM, but the latter does not. In reconstituted vesicles where bR molecules exist as monomer, even sevoflurane forms bR480. Flash photolysis experiments show that bR567 contains a shorter-lived M intermediate absorbing maximally at 412 nm in the photoreaction cycle than bR does and that bR480 contains at least two long-lived M intermediates which seem to absorb maximally near and at lower than 380 nm. The measurements of light-induced pH changes of the whole cells and of the reconstituted vesicles in the presence of the anesthetics indicate that bR567 has a enhanced proton pumping efficiency, while bR480 has a quite low or no activity. No significant difference was observed in the anesthetic action between two inversely pumping vesicles. These observations suggest that on the formation of bR480, anesthetics enter into the membrane and affect the protein-lipid interaction.

X-ray diffraction and flash photolysis studies of M intermediate of lattice-contracted purple membrane.

The effects of cross-linking and lattice contraction of purple membrane (PM) on the photodynamics of bacteriorhodopsin (bR) and on the tertiary structure were studied by flash photolysis and X-ray diffraction. To get a contracted lattice form of PM, native PM, and/or PM cross-linked by glutaraldehyde were treated with deoxycholate or Triton X-100. Part of the Triton-treated cross-linked PM was further incubated with Bio-Beads SM-2 to remove Triton X-100. In the modified PM, several long-lived components of the M intermediate appeared, the features of which were related to the environment of bR. Also, X-ray diffraction studies using synchrotron radiation were performed on the modified PM under intense light irradiation (lambda greater than 500 nm) in which 40-80% of bR was photoconverted to the M state. In the Triton-treated cross-linked PM dispersed in 0.25% Triton X-100, the unit cell of membrane crystalline lattice was enlarged from 58.8 to 59.8 A and the crystalline order decreased with irradiation. The analysis of X-ray diffraction patterns suggests that light-induced conformational changes of bR correlated with the Triton content of the environment and an increase of substitution disorder was caused by these changes, but the average location of bR was unchanged. However, the other modified PM showed no significant changes of diffraction, upon light irradiation.