The intermediate valence state in rare earth compounds; bulk and surface manifestations

X-ray photoelectron spectroscopy (XPS) has made significant contributions to our understanding of the interconfiguration fluctuation (ICF) phenomenon in rare earth solid. ICF behavior has been found in compounds of most of the rare earths which exhibit more than one stable valence state, i.e., Ce, Sm, Eu, Tm and Yb. XPS generally leads to conclusions consistent with those from other measurements. However, it has recently been shown that certain materials which have a stable trivalent state in the bulk undergo a transition to an ICF state at the surface, and that others which have an ICF state in the bulk may have a stable divalent surface.     

The study of electron transfer in advanced materials (electrodes for Li-ion batteries or catalysts)

Mössbauer Spectroscopy (MS) is really suitable to study local electronic structures. Its hyperfine parameters, isomer shift (IS) and quadrupole splitting (QS) allow to characterize the oxidation state and coordination of the probed element. So, the capabilities of this powerful technique have been highlighted for the study of electron transfer occurring during electrochemical or catalytic processes. Several examples illustrate how MS can be used for the determination of reaction mechanisms in new electrode materials of Li-ion batteries (Sb or Sn-based, Ti oxides) or reforming catalysts (supported bimetallic PtSn catalysts). Deeper insight into the mechanisms determining the electrochemical or catalytic performances can be expected.     

SCF MS Xα determination of ionization energies and atomic populations of octaedral TiO-86 cluster

The ionization energies of titanium and oxygen states in BaTiO₃ crystal have been investigated through the self-consistent-field-Xα-scattered-wave (SCF MS Xα) method, with the Slater transition state model, applied to a TiO^?8₆ cluster of octaedral symmetry. Ionization energies and electronic charge distribution are compared to XPS data and related to results obtained from tight-binding band computations.     

Electronic structure of CeRhX (X = Sn,In)

Electronic structure of the compounds CeRhIn and CeRhSn have been studied by the X-ray photoemission spectroscopy (XPS) and ab initio band structure calculations. CeRhSn shows the non-Fermi liquid characteristics at low temperatures, while CeRhIn exhibits a Fermi-liquid ground state. At ambient temperature the XPS data reveal an intermediate valence state of Ce ions in both systems. The Ce core-level XPS spectra are very similar and indicate the strong coupling of the Ce 4f and the conduction band states (Δ ≈ 100 meV). The valence band spectra we interpret with the help of ab initio calculations as well as using the results for the reference compounds LaRhIn and LaRhSn. The comparative analysis of the theoretical band structures and charge density plots reveal the changes in chemical bonding and the hybridization between the Ce 4f and the other valence states introduced by the replacement of In by Sn atoms. The more covalent character of the chemical bonding in the stannides is in line with the smaller thermal expansion. Finally, for CeRhIn we found a typical temperature dependence of the crystal lattice, while CeRhSn shows distinct anomaly at about 120 K, presumably related to the change in planar Ce–Rh bonds.     

XPS Spectra of organometallic phenyl compounds of P,As, Sb and Bi

XPS spectra of 54 organometallic compounds of group V elements with various coordinations are measured in the solid state. Core level binding energy data for the various atoms present in the molecules are given.     

Magnetic susceptibility and Eu Mössbauer studies on cubic ternary compounds: EuPtSi and EuPdSi

Two new equiatomic ternary compounds, EuPtSi and EuPdSi, have been synthesized and are found to crystallize in the cubic LaIrSi type structure. The magnetic susceptibility of both compounds follows Curie-Weiss behavior in the temperature range 10 to 300 K with an effective magnetic moment close to that of Eu²⁺ moment. The paramagnetic Curie temperatures are 5 K for EuPtSi and 9 K for EuPdSi. There is no clear indication of magnetic ordering in the susceptibility of both the compounds down to 4.2 K. However, ¹⁵¹Eu Mössbauer studies show a hyperfine split pattern in EuPtSi at 4.2 K indicating the onset of magnetic ordering. The ¹⁵¹Eu isomer shifts are temperature independent and are characteristic of the divalent Eu ion. All these results establish that the Eu ions are in a stable divalent state in these compounds.     

Structural,magnetic and151Eu Mössbauer studies on EuTCu4 (T-Al,Pd and Ag) compounds

New ternary compounds having the formula EuTCu₄ where T=Al, Pd and Ag have been synthesized. All these compounds are found to crystallize in the hexagonal CaCu₅ type structure. Magnetization measurements reveal that these compounds are magnetically ordered with magnetic moments close to 7 μ_B. The Curie temperatures obtained from low field ac susceptibility measurements are 26K, 25K and 50K for T-Al, Pd and Ag respectively.¹⁵¹Eu Mössbauer studies at room temperature show a large negative isomer shift relative to SmF₃. A hyperfine split pattern is observed at 4.2K in all these compounds, indicating that Eu ion is present in a divalent state and is magnetically ordered.     

Development of 125Te synchrotron-radiation-based Mössbauer spectroscopy

The Mössbauer spectra of the 35.49 keV excited state of ¹²⁵Te were observed in the energy domain using synchrotron radiation for the first time. The obtained isomer shifts and Debye temperature agree with previous experiments. These results show that this method will be applicable to various compounds.     

Relationship between 237Np Mössbauer parameters and bond distances in nitrogen coordinated [NpO2(acac)2py]

We now report the ²³⁷Np Mössbauer spectra for [NpO₂(acac)₂py] I. The neptunium(VI) ion in I is coordinated by six oxygen atoms and the one nitrogen atom of pyridine. The isomer shift value obtained for I is ?40 mm/s, which falls in the range for the Np(VI) oxidation state. The relationship between the isomer shift and Np–O bond distance of the neptunyl group for oxygen coordination compounds is in good agreement with the reported structure of I. It is well known that the mean Np–O bond distance of the neptunium compounds is shorter by 0.01 Å than that of analogous uranium compounds. The good agreement in the ²³⁷Np–Mössbauer parameters and the Np–O distance has indicated that the reported analogous [UO₂(acac)₂py] structure may have some inaccuracies. Therefore, we have re-determined the crystal structure of [UO₂(acac)₂py]. The U–O bond distance we have obtained is reasonable.     

FTIR和XPS对含低价Cr混合物物相分析的应用研究

因Cr的可变价态较多,且在制备低价Cr氧化物过程中,经常出现不同价态的中间体过渡产物,这些过渡产物的性质各异,往往对最终产物的形貌特征产生显著影响。以KCrO₂为原料制备低价Cr化合物的过程中出现了组成比较复杂的中间产物,为探讨反应机理并优化工艺流程,文章结合光电子能谱(XPS),傅里叶变换红外光谱(FTIR),X射线衍射(XRD),电感耦合等离子发射光谱(ICP-AES)元素分析和化学滴定分析对KCrO₂的还原中间产物进行了物相分析。XPS能谱分析表明, 还原中间产物中Cr元素是以三价形态存在的;对不同还原温度所得的中间产物的FTIR与其他方法所得的水合氧化Cr的FTIR进行比较, 并结合XRD测试,元素分析,化学分析结果可以得出下面结论：中间产物主要组成为Cr(OH)₃·nH₂O,CrOOH。还有少量的KOH或KCrO₂。在对中间物相分析的基础上, 对还原过程可能发生的反应进行了推测。