Screening channels in 4f photoemission from light rare earth compounds

The results of valence-band photoemission measurements at the giant 4d-4f resonance are reported for the REIr₂ and RERh₂ series of compounds with RE = Ce, Pr, Nd. Double peaked structures in the 4f derived photoemission spectra are observed in all cases, with roughly constant separation between the two peaks. We propose that the peak closest to the Fermi level results from the occupation of a 4f/5d hybridized screening orbital, with decreasing 4f weight from Ce to Nd systems.     

Photoemission from the valence bands of Ce(1 1 1) on W(1 1 0)

We report a photoelectron spectroscopic study of the valence bands of epitaxial Ce(1 1 1) films grown on W(1 1 0) at room temperature. The evolution of γ → α → γ like phase transition of Ce is observed with increasing Ce coverage and the valence-band structures of γ-like Ce film are determined. The 4f and 5d photoemission cross sections in the photon energy region from 20 eV to 130 eV are presented and discussed. A 5d-like surface state and a 6s band bottom are identified.     

LaOBr:Ce,Tb中Ce3+对Tb3+发光的影响

近年来人们对LaOBr:Tb的合成及其发光特性的研究日益增多。LaOBr:Tb不仅是良好的X光增感屏材料,也是较好的阴极射线发光材料。为了进一步提高它的亮度,降低了b的含量(因Tb很贵),寻求LaOBr中Tb3+发光的敏化剂是很重要的。     

Mixed valence and 4f surface chemical shift in CeN

Resonant photoemission has been used to study the 4f state in single crystal Ce chalcogenides and pnictides. For mixed valent CeN a surface binding energy shift of the 4f state of about 1 eV has been observed. The apparent binding energy of the 4f state in Ce pnictides and Ce chalcogenides differs by as much as 3 eV. Systematic trends in the binding energy are observed. It is suggested that final state screening effects due to 5d electrons, which show the same trends, are responsible for the observed effects.     

Spin-resolved photoelectron spectroscopy of rare-earth overlayers on rare-earth and d-metal substrates

Spin- and angle-resolved photoelectron spectroscopy was applied for studies of electronic and magnetic structures of Eu/Gd and Ce/Fe. Ferromagnetic coupling of 4f moments of Eu and Gd was found in the 1 ML Eu/Gd(0 0 0 1) system with high net Eu magnetization at low temperatures reflected by a spin polarization of 15% of the Eu 4f state. In case of the 1 ML Ce/Fe(1 1 0) system the antiparallel orientation of the Ce 4f spins with respect to the magnetization direction of the Fe substrate was observed. Very different shapes of the spin-up and spin-down Ce 4f spectral weights can be explained within periodic Anderson model by spin-dependent hybridization between Ce localized 4f and itinerant valence band states.     

X-Ray photoemission study of CuIr2S4: Ir3+-Ir4+ charge ordering and the effect of light illumination

We have studied the electronic structure of the spinel-type compound CuIr2S4 using x-ray photoemission spectroscopy (XPS). CuIr2S4 undergoes a metal-insulator transition (MIT) at approximately 226 K. In going from the metallic to insulating states, the valence-band photoemission spectrum shows a gap opening at the Fermi level and a rigid-band shift of approximately 0.15 eV. In addition, the Ir 4f core-level spectrum is dramatically changed by the MIT. The Ir 4f line shape of the insulating state can be decomposed into two contributions, consistent with the charge disproportionation of Ir3+:Ir4+=1:1. XPS measurements under laser irradiation indicate that the charge disproportionation of CuIr2S4 is very robust against photo-excitation in contrast to Cs2Au2Br6 which shows photo-induced valence transition.     

Interconfigurational 5d?→?4f luminescence of Ce(3+) and Pr(3+) in Ca(9)Lu(PO(4))(7)

Ca(9)Lu(PO(4))(7):Ce (3+) and Ca (9)Lu (PO (4))(7):Pr (3+) polycrystalline materials were synthesized by solid state reaction at high temperature. The materials were characterized by powder x-ray diffraction (XRPD). The luminescence spectroscopy and the excited state dynamics of these compounds were investigated upon excitation with UV/VUV synchrotron radiation. Both materials showed efficient and fast 5d-4f emission upon direct VUV excitation into the 5d levels but only Ca(9)Lu(PO(4))(7):Ce (3+) revealed luminescence upon excitation across the bandgap. The decay kinetics of the 5d-4f emission upon VUV intra-center excitation is characterized by a decay time of 29?ns for Ce (3+) and 17 ns for Pr (3+) with no significant build-up after the excitation pulse. For the both compounds, no significant temperature dependence of the 5d-4f emission lifetime was observed within the range 8-300?K.     

First principles study of the magnetism driven by cation defects in CeO₂:the important role of O2p states

The magnetism driven by cation defects in undoped CeO 2 bulk and thin films is studied by the density functional theory corrected for on-site Coulomb interactions (DFT+U) with U = 5 eV for the Ce4f states and U = 7 eV for the O2p states. It is found that the Ce vacancies can induce a magnetic moment of the ～ 4 μ B /supercell, which arises mainly from the 2p hole state of the nearest neighbouring O atom (～ 1 μ B on per oxygen) to the Ce vacancy. The effect of the methodology is investigated, indicating that U = 7 eV for the O2p state is necessary to obtain the localized O2p hole state in defective ceria with cation vacancies.     

Determining the crystal-field ground state in rare earth heavy fermion materials using soft-x-ray absorption spectroscopy

We infer that soft-x-ray absorption spectroscopy is a versatile method for the determination of the crystal-field ground state symmetry of rare earth heavy fermion systems, complementing neutron scattering. Using realistic and universal parameters, we provide a theoretical mapping between the polarization dependence of Ce M(4,5) spectra and the charge distribution of the Ce 4f states. The experimental resolution can be orders of magnitude larger than the 4f crystal-field splitting itself. To demonstrate the experimental feasibility of the method, we investigated CePd2Si2, thereby settling an existing disagreement about its crystal-field ground state.     

Pt/Ce4O8团簇催化活性的第一性原理研究

基于密度泛函理论的第一性原理计算程序包VASP（Vienna ab-initio Simulation Package）,采用投影缀加平面波（Projector augmented wave,PAW）方法和具有三维周期性边界条件的超原胞模型,对Pt在Ce₄O₈团簇上的吸附特性进行了研究,结果表明Pt在Ce₄O₈团簇上的吸附作用很强,其吸附能大于Pt在CeO₂晶体表面的吸附能.所得吸附构型可分为三类:单键类,双键类和多键类.对其中最稳定吸附构型的电子结构分析表明:Pt的吸附诱导出了间隙态.该态距离费米能级很近,使Pt/Ce₄O₈团簇活性很强.Pt与Ce₄O₈团簇发生了部分电荷转移,从而使其中的一个Ce⁴⁺还原为Ce³⁺.这些结果有助于理解在纳米尺度范围内Pt与CeO₂的协同作用.     

Pt/Ce4O8团簇催化活性的第一性原理研究

基于密度泛函理论的第一性原理计算程序包VASP(Vienna ab-initio Simulation Package), 采用投影缀加平面波(Projector augmented wave, PAW)方法和具有三维周期性边界条件的超原胞模型, 对Pt在Ce4O8团簇上的吸附特性进行了研究. 结果表明Pt在Ce4O8团簇上的吸附作用很强，其吸附能大于Pt在CeO2晶体表面的吸附能. 所得吸附构型可分为三类：单键类, 双键类和多键类. 对其中最稳定吸附构型的电子结构分析表明：Pt的吸附诱导出了间隙态. 该态距离费米能级很近，使Pt/Ce4O8团簇活性很强. Pt与Ce4O8团簇发生了部分电荷转移, 从而使其中的一个Ce4+还原为Ce3+. 这些结果有助于理解在纳米尺度范围内Pt与CeO2的协同作用.     

CaAl3BO7：RE(RE=Ce,Gd,Tb)中稀土离子的光谱特性

采用固相反应法合成了CaAl₃BO₇RE(RE=Ce,Gd,Tb),研究了Ce³⁺,Gd³⁺和Tb³⁺的光谱特性。发现铈离子周围存在较强的晶场,使基态的4f能级劈裂较大,从而导致铈离子的特征发射峰重叠较大;Ce³⁺的5d能级明显低于Gd³⁺的⁶I、⁶P能级;Ce³⁺和Tb³⁺之间存在有效的能量传递。     

First principles study of the electronic structures of erbium silicides with non-frozen 4f treatment

The electronic structures (especially 4f states) of hexagonal and tetragonal erbium silicides are investigated within density functional theory. Contrary to previous theoretical studies on these compounds, Er 4f electrons are treated as valence state electrons, explicitly taking into account the on-site Coulomb interactions. Total energy calculations show that the relaxed hexagonal ErSi_1.7 is more stable than the tetragonal structure, consistently with related experimental observations. The calculated total density of states of the hexagonal ErSi_1.7 agrees well with the experimental valence-band spectrum in a wide energy range from 0 to 12 eV below the Fermi level. In addition, our study indicates that the occupied 4f states in erbium silicides can also locate in the energy range of 0–4.0 eV below the Fermi energy, much different from the prediction of the previously adopted Er ion model.     

Direct observation of dispersive Kondo resonance peaks in a heavy-fermion system

Ce 4d-4f resonant angle-resolved photoemission spectroscopy was carried out to study the electronic structure of strongly correlated Ce 4f electrons in a quasi-two-dimensional nonmagnetic heavy-fermion system CeCoGe1.2Si0.8. For the first time, dispersive coherent peaks of an f state crossing the Fermi level, the so-called Kondo resonance, are directly observed together with the hybridized conduction band. Moreover, the experimental band dispersion is quantitatively in good agreement with a simple hybridization-band picture based on the periodic Anderson model. The obtained physical quantities, i.e., coherent temperature, Kondo temperature, and mass enhancement, are comparable to the results of thermodynamic measurements. These results manifest an itinerant nature of Ce 4f electrons in heavy-fermion systems and clarify their microscopic hybridization mechanism.     

f-State occupancy at the gamma-alpha phase transition of Ce-Th and Ce-Sc alloys

Resonant inelastic x-ray scattering spectra were measured for a series of Ce solid solutions (Ce-Th and Ce-Sc) across the gamma-alpha phase transition. They reveal a well-defined feature associated with the 4f2 configuration when the incident energy is tuned to the Ce L3 preedge region. This component is normally hidden in x-ray absorption spectra because of lifetime broadening. The f1/f2 ratio estimated by resonant inelastic x-ray scattering presents a sharp drop across the gamma-alpha transition and hysteresis as a function of temperature that closely resemble the magnetization loop. These measurements confirm recent dynamical mean-field theory calculations that unexpectedly predict significant double occupancy of f orbitals in the ground state.     

铈激活磷光体的发光特性

Ce3+的发光属于f-d跃迁,它的荧光寿命非常短,发射光谱呈现带状,并随着基质的不同,发射峰位置发生显著的变化,能从紫外一直到可见区.Ce3+发射峰位置的变化与基质中直接配位的阴离子、阳离子以及阴离予基团等的变化有关,也受晶场劈裂、Stokes位移的影响.Ce3+发射峰位置的变化与化台物的共价程度有关,并得到一些规律性的结果,这将为材料设讨提供依据.文中对一些典型的Ce3+的能量传递和敏化作用作了介绍.     

Physical properties and crystal chemistry of Ce2Ga12Pt

Single crystals of the new ternary compound Ce(2)Ga(12)Pt were prepared by the self-flux technique. The crystal structure with the space group P4/nbm was established from single crystal x-ray diffraction data and presents a derivative of the LaGa(6)Ni(0.6) prototype. Magnetic susceptibility measurements show Curie-Weiss behaviour due to local Ce(3+) moments. At high temperatures, the magnetic anisotropy is dominated by the crystal-electric-field (CEF) effect with the easy axis along the crystallographic c direction. Ce(2)Ga(12)Pt undergoes two antiferromagnetic phase transitions at T(N,1) = 7.3 K and T(N,2) = 5.5 K and presents several metamagnetic transitions for the magnetic field along c. Specific-heat measurements prove the bulk nature of these magnetic transitions and reveal a doublet CEF ground state. The 4f contribution to the resistivity shows a broad maximum at T(max) ≈ 85 K due to Kondo scattering off the CEF ground state and excited levels.     

Probing the transition in bulk Ce under pressure: a direct investigation by resonant inelastic X-ray scattering

We report on the most complete investigation to date of the -electron properties at the transition in elemental Ce by resonant inelastic x-ray scattering (RIXS). The Ce 2p3d-RIXS spectra were measured directly in the bulk material as a function of pressure through the transition. The spectra were simulated within the Anderson impurity model. The occupation number n(f) and f double occupancy were derived from the calculations in both gamma and alpha phases in the ground state. We find that the electronic structure changes result mainly from band formation of 4f electrons which concurs with reduced electron correlation and increased Kondo screening at high pressure.     

First principles study of the magnetism driven by cation defects in CeO2: the important role of O2p states

The magnetism driven by cation defects in undoped CeO2 bulk and thin films is studied by the density functional theory corrected for on-site Coulomb interactions （DFT＋U） with U = 5 eV for the Ce4f states and U = 7 eV for the O2p states. It is found that the Ce vacancies can induce a magnetic moment of the -4 gB/supercell, which arises mainly from the 2p hole state of the nearest neighbouring O atom （-1μB on per oxygen） to the Ce vacancy. The effect of the methodology is investigated, indicating that U = 7 eV for the O2p state is necessary to obtain the localized O2p hole state in defective ceria with cation vacancies.     

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.