3s- and 3p-core level excitations in 3d-transition metal oxides from electron-energy-loss spectroscopy

3s- and 3p-core level excitations for a large number of 3d-transition metal oxides, with a formal 3d occupation from 3d⁰ to 3d¹⁰, have been measured by electron energy loss spectroscopy in reflection geometry (REELS) with primary energies 200 eV≤E ₀≤1600 eV. Their intensities decrease systematically with the formal 3d-count, classifying them as transitions to empty 3d-states. The structure of the 3s excitations is analysed in detail and is compared to the 3s-XPS photoemission spectra of the samples. This 3s-REELS structure and its change with the 3d occupation can be explained by the assumption that the excitation arises mainly from a 3s²3dⁿ→3s¹3dⁿ⁺¹ quadrupole transition.     

Pressure dependent optical absorption edge shift and compressibility of CdCr2Se4 single crystals

The pressure shift of the optical absorption edge (dE_g/dp = (1.1 ± 0.1) × 10^?6 eV bar^?1) and the compressibility (κ = (1.3 ± 0.) × 10^?6 bar^?1) of single crystalline CdCr₂Se₄ have been measured at ambient temperature. These data suggest an interpretation of the fundamental absorption in terms of either p → p interband or p → localized d charge transfer transitions, but exclude excitations involving s-band states.     

The electronic structure of KMnO4 investigated by photoemission and electron-energy-loss spectroscopy

From photoemission and electron-energy-loss data the following picture of KMnO₄, with Mn^VII (with a formal charge state Mn⁷⁺ (3d ⁰)) tetrahedrally surrounded by four O^2–-ions, is deduced: strong covalent bonding between Mn^VII and O^2– leads to a considerable occupation of the Mn-3 d shell. The ground state of the (MnO₄)^–1 molecule is an orbital and spin singlet as seen by the absence of any multiplet splitting in the Mn core levels. The valence band shows a four peak structure extending form 4 eV to 8 eV below the Fermi energy. The first peak at 4.2 eV has mainly O-2p character. The remaining peaks are of strongly mixed Mn-3d/O-2p character due to the covalent bonding. This mixing decreases with increasing binding energy. The electron energy loss data show a variety of structures between 2 eV and 10 eV independent of the primary electron energy which defines them as dipole allowed charge-transfer transitions. An additional excitation at 1.8 eV decreases quickly in intensity with increasing electron energy which classifies it as a dipole or spin forbidden transition in the compound. This energy is close to the value of 1.6 eV reported for the activation energy observed in electrical transport data. The results are compared to quantum chemical molecular orbital calculations of the (MnO₄)^–1 molecule.Physics Department, Allahabad University Allahabad 211002, India     

Species formed at cuprite fracture surfaces; observation of O 1s surface core level shift

Surfaces of mineral cuprite prepared by fracture under UHV have been characterised by synchrotron XPS and near-edge X-ray absorption spectroscopy before and after exposure to ambient air. Before exposure of the cuprite, the Cu 2p photoelectron and Cu L_2,3-edge absorption spectra were consistent with Cu^I with very little d⁹ character. Surface-enhanced O 1s spectra from the unexposed mineral revealed a surface species, with binding energy 0.95 ± 0.05 eV below the principal cuprous oxide peak, assigned to under-coordinated oxygen. A second surface species, with binding energy about 1 eV higher than the principal peak, was assigned to either hydroxyl derived from chemisorbed water vapour or surface oxygen dimers produced by restructuring of the cuprite fracture surface. The width of the principal O 1s peak was 0.66 ± 0.02 eV. The observed Cu L₃- and O K-edge absorption spectra were in good agreement with those simulated for the cuprite structure. After exposure of the fracture surface to ambient air, the low binding energy O 1s surface species was barely discernible, the original high binding energy O 1s surface species remained of comparable intensity, new intensity appeared at an even higher (∼1.9 eV) binding energy, and the Cu L_2,3-edge spectrum indicated the presence of Cu^II, consistent with the formation of a thin surface layer of Cu(OH)₂.     

Luminescence characteristics of the Pr3+ ion in SrAlF5

The paper reports on a study of luminescence and excitation spectra of SrAlF₅:Pr³⁺ (0.5 mol %) polycrystals performed at 10 and 300 K with synchrotron radiation in the range from 5 to 25 eV. The Pr³⁺ ions in SrAlF₅ were shown to emit successively two photons in transitions from the ¹ S ₀ and ³ P ₀ levels. The main energy characteristics of the compound, namely, the position of the 4f → 5d excitation band (5.95–8.0 eV), the energy separation between the ¹ S ₀, 4f and the lowest 5d levels (～0.15 eV), and the SrAlF₅ band gap width (～12 eV), were determined. SrAlF₅:Pr³⁺ was found to possess a number of features not found in other Pr³⁺-activated fluorides.     

Electron energy loss spectra of a Pd(110) clean surface

Electron energy loss spectra of a Pd(110) clean surface have been measured at primary energies of 40–100 eV. The observed peaks are at the loss energies of ∼ 3, 4.3, 7.5, 11.5, 16, 21.3, 26.5 and 33.8 eV. The 7.5, 26.5, and 33.8 eV peaks are attributed mainly to the bulk plasmon excitations associated with 5s electrons, coupled 5s and a limited number of 4d electrons, and total (4d+5s) electrons, respectively. The rest of the peaks are ascribed mainly to one-electron excitations.     

Dissociative multiple photoionization of Br2, IBr,and I2 in the VUV and X-ray regions: a comparative study of the inner-shell processes involving Br(3d,3p,3s) and I(4d,4p,4s,3d,3p)

Dissociative multiple photoionization of the bromine, the iodine monobromide, and the iodine molecules in the Br(3d,3p,3s) and I(4d,4p,4s,3d,3p) inner-shell regions has been studied by using time-of-flight (TOF) mass spectrometry coupled to synchrotron radiation in the ranges of 90∼978 eV for Br₂, 60∼133 eV for IBr, and 86∼998 eV for I₂. Total photoion and photoion–photoion coincidence (PIPICO) yields have been recorded as functions of the photon energy. Here, giant shape resonances have been observed beyond the thresholds of the inner-shells owing to the Br(3d¹⁰)→Br(3d⁹ϵf), I(4d¹⁰)→I(4d⁹ϵf), and I(3d¹⁰)→I(3d⁹ϵf) transitions. The dissociation processes of the multiply charged parent ions have also been evaluated from variations of photoelectron–photoion coincidence (PEPICO) and PIPICO spectra with the photon energy. From each Br(3p_3/2) (189.9 eV) and I(4p_3/2) threshold (129.9 eV), quintuple ionization of the molecules begins to play important roles in the photoionization, subsequently yielding ion pairs of X³⁺–X²⁺ (X=Br, I). From the I(3d_5/2) threshold (627.3 eV), loss of six electrons from iodine molecule additionally begins to play a minor role in the multiple photoionization, giving rise to the formation of ion pairs of either I³⁺–I³⁺ or I⁴⁺–I²⁺. A direct comparison of the strengths and the ranges of the I(4d) and Br(3d) giant resonances was successfully made from dissociative photoionization of IBr. Over the entire energy range examined, 60<E<133 eV, biased charge spread relevant to the specific core-hole states of IBr is observed, presumably reflecting the fact that charge localizes mostly in the excited atoms, which can be accounted for mainly by a two step decay via a fast dissociation followed by autoionization upon the VUV absorption.     

Photoemission studies of single crystals of titanium carbide

The electron distribution in the valence band from single crystals of titanium carbide has been studied by photoelectron spectroscopy with photon energies h?ω = 16.8, 21.2, 40.8 and 1486.6 eV. The most conspicious feature of the electron distribution curves for TiC is a hybridization between the titanium 3d and carbon 2p states at ca. 3–4-eV binding energy, and a single carbon 2s band at ca. 10 eV. By taking into account the strong symmetry and energy dependence of the photoionization crosssections, as well as the surface sensitivity, we have identified strong emission from a carbon 2p band at ? 2.9-eV energy. Our results are compared with several recent energy band structure calculations and other experimental data. Results from pure titanium, which have been used for reference purposes, are also presented.The valence band from single crystals of titanium carbide have been studied by means of photoelectron spectroscopy, with photon energies ranging from 16.8 to 1486.6 eV.By taking into account effects such as the symmetry and energy dependence of the photoionization cross-sections and surface sensitivity, we have found the valence band of titanium carbide to consist of two peaks. The upper part of the valence band at 3–4 eV below the Fermi level consists of a hybridization between Ti 3d and C 2p states. The C 2p states observed in our spectra were mainly excited from a band about 2.9 eV below the Fermi level. The APW^5–9, MAPW¹⁰ and EPM¹¹ band structure calculations predict a flat band of p-character between the symmetry points X′₄ and K₃, most likely responsible for the majority of C 2p excitations observed. The C 2s states, on the other hand, form a single band centered around ?10.4 eV.The results obtained are consistent with several recent energy band structure calculations^{5–11, 13} that predict a combined bonding of covalent, ionic and metallic nature.     

铁电单晶0.62Pb(Mg1/3Nb2/3)O3-0.38PbTiO3折射率的研究

用最小偏向角法在20℃下精确测量了0.62Pb(Mg_1/3Nb_2/3)O_{3< /sub>-0.38PbTiO3( 0.62PMN-0.38PT)单晶的折射率，给出了该温度下折射率色散的Sellmeier方程.研究了能带 结构与折射率的关系，计算了样品的Sellmeier光学系数：对no，E0=5.50eV,λ0=0.2 26μm，Ｓ０=1.004×10¹⁴m^-2，Ed=28.1 0eV；对ne，Ｅ0=5.57eV,λ 0=0.223μm，S0=1.017×10¹⁴m^-2，Ed=28.10eV.A BO3型钙钛矿材料中，BO6八面体基元决定了晶体的能带结构，对折 射率产生重要影响. 关键词： PMNT单晶 折射率 Sellmeier光学系数}     

Laser photoelectron spectrometry of Sc− and Y−: A determination of the order of electron filling in transition-metal anions

The photoelectron spectra of Sc^? and Y^? have been obtained in a crossed ion- and laser-beam experiment. Analysis of the Sc^? spectrum yields two bound terms of 3d4s² 4p configuration (¹D⁰ and ³D⁰), with EA(Sc) = 0.189 ± 0.020 eV and an excited-state binding energy of 0.042 ± 0.020 eV. Similarly, the (4d5s² 5p) ¹D⁰ ground state of Y^?is bound by 0.308±0.012eV and a (4d5s²5P)³D⁰ excited term is bound by 0.165± 0.025 eV. With the determination of the bound electronic configuration of Sc^? as 3d4s²4p, the order of filling of electron shells of the first transition series negative ions is found to be 4s²4p, 3d4s²4p, followed by 3d^k4s² (k = 3,4,…, 10).     

Resonant electron impact excitation of highly charged Fe ions studied with a compact electron beam ion trap

We present extreme ultraviolet spectra of 3s3p–3s3d transitions in Fe¹⁴⁺ observed with a compact electron beam ion trap. The contributions of indirect excitation via a metastable state and resonant excitation are studied by observing the electron energy dependence of the spectra for the energy range of 60–210 eV. The results indicate that the 3s3d ¹D₂ level is directly excited from the 3s² ground state whereas the 3s3d ³D₃ level has a large contribution of the indirect excitation via the 3s3p ³P₂ metastable state. Comparisons with the theoretical excitation cross sections including MNn resonant excitations show good qualitative agreement with the experimental results for the electron energy dependent features.     

Laser-rf double-resonance hyperfine structure measurements of the metastable 3d 4s 1 D 2 state of43Ca

The hyperfine structure of the (3(d 4s)¹ D ₂metastable state of⁴³Ca has been measured using theABMR-LIRF method (atomic beam magnetic resonance, detected by laser induced resonance fluorescence). The measurements yielded for the magnetic dipole and electric quadrupole constantsA=?17.650(2) MHz andB=?4.642(12) MHz, respectively. From the measuredB factor the spectroscopic electric quadrupole moment (uncorrected for shielding effects) has been calculated to beQ(⁴³Ca)=?0.062(12) barn. In addition, isotope shifts in the lines (3d 4s)¹ D ₂(3d 4p)¹ F ₃ ⁰ and (3d 4s)¹ D ₂(4s 5p)¹ p ₁ ⁰ for the stable calcium isotopes have been obtained by high resolution laser spectroscopy.     

类铷W37+离子双电子复合速率系数的理论研究

 利用全相对论组态相互作用理论方法,研究了类铷W³⁷⁺离子从基组态3s²3p⁶3d¹⁰4s²4p⁶4d经过双激发态(3s²3p⁶3d¹⁰4s²4p⁶4d)^-1nln′l′(n,n′=4,5)的双电子复合过程,得到了该离子在温度为1~5×10⁴ eV范围内的总双电子复合速率系数。分析比较了不同电子激发的双电子复合速率系数,结果表明:4p电子激发的双电子复合速率系数在低温时给出了主要贡献,而3d的贡献在高温时突出。由于强组态相互作用,两电子一光子跃迁对双电子复合速率系数的贡献不可忽略,其中辐射跃迁4p⁵4d5d5f-4p⁶4f5d的贡献是双激发态4p⁵4d5d5f总的双电子复合速率系数的5%。对双电子复合、辐射复合以及三体复合速率系数的比较表明,在所研究的温度范围内双电子复合速率系数最大。     

Improved infrared and visible emission spectra of the H3 and D3 molecules

Better-resolved Rydberg-Rydberg emission spectra of the neutral H₃ and D₃ molecules in the infrared and visible regions, with less interference from H₂ and D₂ emission, have been obtained by using a Droege-Engelking type of corona discharge source. Using nl_λ notation, the lower electronic states are 3p₁ in the infrared and 2p₀ in the visible, and the upper electronic states are mixed (3s,3p₀,3d₀,3d₁,3d₂) states. In particular, a line near 16 842 cm⁻¹ in H₃, previously obscured by an H₂ line, reveals a (3s,3d) interaction that is confirmed by other lines. The spectra are analysed including this interaction. However, fits to effective Hamiltonians still have relatively large standard deviations, probably partly due to poor convergence of the rotational expansions and partly due to many small perturbations of the levels by background states.     

Electron energy-loss spectroscopy of UHV-cleaved NiO (100) surfaces

Electron energy-loss spectroscopy of ～ 200 eV electrons has been applied to the study of the electronic states of clean NiO (100) surfaces. Initial attempt has been made on the identification of observed peaks, and they are attributed to the one-electronic transitions (O^2-2p → Ni²⁺3d, 4s and 4p; Ni²⁺3d → 4p, 3p → 3d and 4s), and the collective excitations (bulk plasmons of O^2-2p, Ni²⁺3d electrons, and coupled 2p and 3d electrons).     

A facile one-pot solvothermal route to tubular forms of luminescent polymeric networks [(C3N3)2(NH)3]n

A facile one-pot solvothermal route has been developed for the synthesis of tubular luminescent polymeric networks [(C₃N₃)₂(NH)₃]_n, structurally related to the proposed g-C₃N₄. XRD patterns showed a characteristic 002 basal plane diffractions, indicating an interlayer d spacing of 3.23 Å. XPS spectra show that the C1s and N1s have a symmetric peak and an asymmetric peak at 288.10 and 399.00 eV, respectively. The bulk composition C₆N_8.9H_4.5 determined by elemental analysis is comparable to the calculated value C₆N₉H₃ for this proposed polymer. FTIR spectra indicated the presence of s-triazine ring, which was further supported by the luminescent and UV-vis absorption characteristics probably depending on π→π^* electronic transition. The tubular structure has been studied by TEM, SAED, and HREM.     

Optical investigation of charge-transfer transitions in spinel Co3O4

Optical transitions in normal-spinel Co₃O₄ have been identified by investigating the variation of its optical absorption spectrum with the replacement of Co by Zn. Three optical-transition structures were located at about 1.65, 2.4, and 2.8 eV from the measured dielectric function of Co₃O₄ by spectroscopic ellipsometry. The variation of the absorption structures with the Zn substitution (Zn_xCo_3−xO₄) can be explained in terms of charge-transfer transitions involving d states of Co ions. The 1.65 eV structure is assigned to a d-d charge-transfer transition between the t_2g states of octahedral Co³⁺ ion and t₂ states of tetrahedral Co²⁺ ion, t_2g(Co³⁺)→t₂(Co²⁺). The 2.4 and 2.8 eV structures are interpreted as due to charge-transfer transitions involving the p states of O²⁻ ion: p(O²⁻)→t₂(Co²⁺) for the 2.4 eV absorption and p(O²⁻)→e_g(Co³⁺) for the 2.8 eV absorption. The observed gradual reduction of the 1.65 and 2.4 eV absorption strength with the increase of the Zn composition for Zn_xCo_3−xO₄ can be explained in terms of the substitution of the tetrahedral Co²⁺ sites by Zn²⁺ ions. The crystal-field splitting Δ_Oh between the e_g and the t_2g states of the octahedral Co³⁺ ion is estimated to be 2 eV.     

Stopping power of low-energy deuterons in 3He gas

The stopping power of atomic and molecular deuterons in ³He gas was measured over the range E _d = 10 to 100 keV using the ³He pressure dependence of the ³He(d,p) ⁴He reaction yield. At energies above 30 keV, the observed stopping power values are in good agreement with a standard compilation. However, near 18 keV the experimental values drop by a factor 50 below the extrapolated values of the compilation. In a simple model, the behavior is due to the minimum 1s↦2s electron excitation of the He target atoms (= 19.8 eV, corresponding to E _d = 18.2 keV), i.e. it is a quantum effect, by which the atoms become nearly transparent for the ions.