Infrared studies of lithium intercalation in the FePS3 and NiPS3 layer-type compounds

Infrared spectra (700-30 cm^-1) of several lithium intercalates (chemically prepared) Li_xMPS₃, with M=Fe, Ni and 0<x<1.5, have been recorded and compared with those known for the corresponding host lattices. These lithium intercalates are mainly characterized by new absorption bands at 336 cm^-1 and 310 cm^-1 for the iron and nickel compounds, respectively. These bands assigned to lithium vibrations increase progressively with lithium content : it is concluded that Li⁺ ions are more likely to occupy the 2d and 4h “octahedral” sites in the gaps. In addition, the spectra of the nickel derivatives reveal some geometric distortion within the layers and a progressive strengthening of the Ni-S interactions. These results are correlated to the best energy yields obtained in NiPS₃/lithium batteries.     

Soft vibrational mode in LiNbO3 and LiTaO3

The temperature dependence of the far-infrared reflectivity as obtained with a scanning interferometer for the A₁- and E-type modes of both LiNbO₃ and LiTaO₃ is reported in the ferroelectric phase. Results of a Kramers-Kronig analysis are compared with Raman and neutron scattering data which are controversial about the existence of a soft vibrational mode. For LiTaO₃, spectra are obtained 300 K above the Curie temperature, in the paraelectric phase. The lowest-frequency A₁ (TO) mode is unambiguously found as soft and becomes rapidly overdamped.     

Hydrogen absorption in CeFe2 and ThFe3

The effect of hydrogen absorption on the magnetic properties of CeFe₂ and ThFe₃ was studied by magnetization measurements and by the ⁵⁷Fe Mössbauer effect. In both cases an increase in the transition metal moment is observed. In CeFe₂ the long range periodicity of the crystal lattice is lost whereas in ThFe₃ a structural change occurs. Surprisingly, the magnetic anomaly observed in ThFe₃ around 250 K is still present in the hydride.     

The local electronic structure of PdO crystal and PdO catalyst supported on SiO2 and γ-Al2O3 from L3 and L1 x-ray absorption Pd edge in XANES spectra

We have studied the local electronic structure of PdO catalysts supported on characteristic inert and quasi-inert substrate from experiment on X-ray absorption near edge structure XANES using Synchrotron radiation. From the joint analysis of L₃ absorption edge and XPS core data in Pd and PdO we find that the white line in PdO XANES is an excitonic state with 0.8 eV binding energy. From the joint analysis of L₃ and L₁ edges the p-like and the d-like local unoccupied electronic states have been determined. The local structure of PdO catalysts is different from that of PdO crystal. Evidence for structural disorder in PdO catalysts and PdO-substrate interaction is reported.     

Calorimetric and x-ray diffraction studies of the (NH4)3WO3F3 and (NH4)3TiOF5 perovskite-like oxyfluorides

The heat capacity and unit cell parameters of the (NH₄)₃WO₃F₃ and (NH₄)₃TiOF₅ perovskite-like oxyfluorides were measured in the temperature interval from 80 to 300 K; the existence of two and one phase transitions in these compounds, respectively, was demonstrated, and their thermodynamic parameters were determined. The effect of a hydrostatic pressure of up to 0.5 GPa on the phase transition temperatures was studied. Triple points and high-pressure phases were found in the T vs. p diagrams. An analysis of entropy changes suggests that all the structural transformations revealed are associated with the ordering of structural blocks. __________ Translated from Fizika Tverdogo Tela, Vol. 46, No. 5, 2004, pp. 888–894. Original Russian Text Copyright ? 2004 by Flerov, Gorev, Fokina, Bovina, Laptash.     

Magnon absorption and luminescence in CsMnF3

We report observations of multimagnon sidebands of the excitonic transition in CsMnF₃ using polarized absorption and time resolved spectroscopy technics. The results are discussed in terms of exchange interaction (single particle model) and magnon density of states (magnon frequencies).     

Splitting of the near infrared absorption bands of Sm in POCl3:SnCl4, POCl3:ZrCl4 and POCl3:TiCl4

The near infrared absorption spectra of Sm³⁺ in POCl₃:SnCl₄, POCl₃:ZrCl₄ and POCl₃:TiCl₄ consist of a series of bands, attributed to the ⁶H_5/2 → ⁶F_J transitions. Each one of these absorption bands is split into three components. The extent of splitting differs slightly from state to state. For each component of the ⁶F-multiplet the splitting decreases gradually from POCl₃:SnCl₄ to POCl₃:ZrCl₄ and POCl₃:TiCl₄. Energy differences between adjacent components of the near infrared absorption bands vary from a maximum of 166 cm⁻¹ to a minimum of 123 cm⁻¹. The band half-widths of the corresponding components vary from 86 to 120 cm⁻¹. At lower temperatures the intensity of the high energy component increases whereas the intensity of the entire absorption band envelope, associated with each component of the ⁶F-multiplet, remains almost constant. The splitting observed is attributed to the Stark splitting of the ⁶H_5/2-state of Sm³⁺ into three components, in conjunction with appropriate Stark splitting of the states of the ⁶F-multiplet.     

Single-crystal absorption and emission spectra of CsVCl3 and CsMgCl3:V2+

Single-crystal absorption and emission spectra of CsVCl₃ and CsMgCl₃:V²⁺ in the region of the first excited state were measured at temperatures down to 6 K. The ⁴A_2g?⁴T_2g transition shows a large trigonal splitting of the ⁴T_2g state and surprisingly well-resolved fine structure which can be analyzed in terms of electronic origins and vibronic side bands.     

Loss of ferromagnetism in YNi3 after H2 absorption

The compound YNi₃ ($\text{PuNi}{}_3\text{-}\text{type}\text{,}\text{a}\text{= 4.973}\text{A}\text{?}\text{,}\text{c}\text{= 24.42}\text{A}\text{?}$) is ferromagnetic below T_c = 35 K. After hydrogen absorption it loses its ferromagnetic character and becomes Pauli paramagnetic. The composition of the ternary hydride is approximately YNi₃H₄. The lattice constants are $\text{a}\text{= 5.267}\text{A}\text{?}$, $\text{c}\text{= 26.57}\text{A}\text{?}$.     

Farinfrared absorption in Al2O3 and MgO

Far-infrared absorption measurements performed in Al₂O₃ and MgO between 300 and 1 500 K with a Fourier scanning interferometer are reported. A temperature analysis of results based on a phonon self-energy model allows to assign the absorption in this region to 2- and 3-phonon difference processes. The contributions of these processes are separated and discussed. In Al₂O₃, the frequency dependence of the absorption is also analyzed. A good overall agreement between theory and experiment is evidenced.     

Excited-state absorption of Co2+ in MgF2 and KZnF3

We report on measurements of excited-state absorption spectra and absolute cross-sections in Co²⁺-doped KZnF₃ and MgF₂ at room temperature in the near-infrared domain. The data are compared with the predictions of the single-configuration co-ordinate model.     

Soft pion solution of Kl3 parameters

A new soft-pion relation involving the K_l3 form-factors is proposed. Together with the well-known soft pion theorem, a solution of the K_l3 parameters is obtained under various assumptions of linearity of form-factors.     

The ν3 and 2ν3 bands of SO3, SO3, SO3, and SO3

This sixth of a series of publications on the high-resolution rotation-vibration spectra of sulfur trioxide reports the results of a systematic study of the ν₃ and 2ν₃ infrared bands of the four symmetric top isotopomers ³²S¹⁶O₃, ³²S¹⁸O₃, ³⁴S¹⁶O₃, and ³⁴S¹⁸O₃. An internal coupling between the l=0(A₁^′) and l=2(E^′) levels of the 2ν₃ states was observed. This small perturbation results in a level crossing between |k−l|=9 and 12, in consequence of which the band origins of the A₁^′,l=0 “ghost” states could be determined to a high degree of accuracy. Ground and upper state rotational constants as well as vibrational anharmonicity constants are reported. The constants for the center-of-mass substituted species ³²S¹⁶O₃ and ³⁴S¹⁶O₃ vary only slightly, as do the constants for the ³²S¹⁸O₃, ³⁴S¹⁸O₃ pair. The S-O bond lengths for the vibrational ground states of the species ³²S¹⁶O₃, ³⁴S¹⁶O₃, ³²S¹⁸O₃, and ³⁴S¹⁸O₃ are, respectively, 141.981 99(1), 141.979 38(6), 141.972 78(8), and 141.969 93(8) pm, where the uncertainties, given in parentheses, are two standard deviations and refer to the last digits of the associated quantity.     

X-ray L1, L2 and L3 absorption limits of 4D transition metals

The wavelengths and energies of the L₁, L₂ and L₃ absorption limits in Zr, Nb, Ru, Rh, Pd and Ag metals have been measured and some of the previous reported values have been found to be incorrect. By comparing the energies of the absorption limits with those of the Lγ₁Ly, and Lβ_2,15, lines and also with the binding energies obtained by XPS, the electronic transitions corresponding to the respective absorption limits have been clarified. It is concluded that (i) the end level of the electronic transition corresponding to the L₁ absorption limit of Zr-Ag is the 5p-like level, and (ii) the end level corresponding to either of the L₂ and L₃, absorption limits of Zr-Pd is the 4d level, while that of Ag is, rather unexpectedly, the top of the 5s level.     

Time-resolved optical absorption in YAlO3 crystals

The present work is devoted to the investigation of transient absorption (TA) induced by a pulsed electron beam (E=250 keV) in pure and doped YAlO₃ (YAP) single crystals. The nature of centers responsible for TA is discussed.     

Optical absorption spectrum and local symmetry of Tm ion in TmAl3(BO3)4 crystal

With the help of group theory analysis of absorption spectra of the transition ³H₆ → ³F₃ of Tm³⁺ ion in TmAl₃(BO₃)₄ crystal, measured at several temperatures from 1.8 till 293 K, it has been shown, that the local symmetry of the Tm³⁺ environment is C₃ and it decreases to C₁ at a low temperature. Effective selection rules and polarizations of lines at high enough temperatures (when the line-width is larger than the splitting in C₃ symmetry) have been obtained.     

Low-temperature absorption contour of the ν3 band of SF6

A band contour analysis is carried out for the ν₃ absorption in SF₆. Values of ΔB = ? (1.0 ? 1.5) × 10^?4cm^?1, ζ₃ = 0.701, and ν₀ = 948.2cm^?1 are found. Tentative assignments are given for the SF₆ rotational states which are pumped by the P(14) through P(22) lines of the CO₂ laser.     

4f ground state properties of cerium in AuCu3 intermetallic compounds studied by x-ray absorption spectroscopy

L_III absorption edges of cerium in ternary AuCu₃ compounds Ce(Pd_1?xM_x)₃ (M = Ag and Rh) and (Ce_1?xY_x)Pd₃ are presented. We find that Ce in these compounds is mixed valent with n_f ? 0.7. The valence V of Ce(Pd_1?xRh_x)₃ becomes concentration independent of V = 3.29 ± 0.02 for x ? 0.18. In Ce_1?xY_xPd₃ we observe the valence to increase up to V = 3.32 ± 0.02 at the highest concentration of Y. We show, that a critical volume, available for the Ce atom, is associated with the concentration independent valence around 3.3. For both systems, linewidths W₁, W₀ and Δ = E(4f¹) ? E(4f⁰), as derived from L_III double-bump structure, are given. Possible falsifications due to “final states effects” on the valence are discussed.     

金属纳米团簇复合薄膜Au/BaTiO3与Fe/BaTiO3的PLD制备及其光吸收特征

用脉冲激光沉积技术制备了掺杂纳米金属颗粒Au或Fe的BaTiO₃复合薄膜.用透射电子显微镜和x射线光电子能谱表征了金属颗粒的形态和化学态.330—800nm范围的吸收谱研究表明，掺Au颗粒的BaTiO₃薄膜在580nm附近有一个明显的共振吸收峰，而掺Fe颗粒的BaTiO₃薄膜没有这样的吸收峰.用Mie散射理论对结果进行了分析. 关键词： 复合薄膜 金属颗粒 脉冲激光沉积 吸收谱