Charge transfer transition accompanying x-ray photoionization in transition-metal compounds

Satellites, 5 to 10 eV below the main peaks, have been observed in the x-ray photoelectron spectra of the 2s, 2p, 3s, 3p and valence shells of the 3d transition-metal ions of nickel and copper oxides. They are believed to be the result of electron shake-up. Since shake-up satellites are present in ions with partially filled 3d shell but absent in ions with completely filled 3d shell, they may be attributed to monopole charge transfer transitions (ligand → metal 3d) using the sudden approximation (monopole selection rules) and the ligand field theory.     

Magnetic dichroism in K-shell photoemission from laser excited Li atoms

Magnetic dichroism in the angular distribution has been demonstrated for single-electron photoemission from inner ns(2) subshells of gaseous atomic targets using the example of K-shell photoionization of polarized Li atoms laser prepared in the 1s(2)2p (2)P(3/2) excited state. The effect is pronounced for the conjugate shakeup and conjugate shakedown photoelectron lines, and less important, though observable, for the main and direct shakeup lines. The phenomenon is caused by configuration interaction in the final continuum state and is quantitatively described by the close-coupling R-matrix calculations.     

A complete and self-consistent evaluation of XPS spectra of TiN

The electron configuration in single crystalline (sc-)titanium nitride (TiN) has been quantitatively studied using angle resolved X-ray photoelectron spectroscopy (AR-XPS). All samples were fabricated and transferred in situ so that only minimal surface contaminations were observed. The residual oxygen contamination was separated from the bulk information by extrapolating angle resolved measurements. Special attention is given to the quantitative evaluation of the spectra based on basic principles. Shake-up features are observed on core level lines and appear due two final ionized states. The ratio of this shake-up and the main Ti 2p energy line are investigated in this paper. In order to quantify this shake-up a precise evaluation is required. Here we present an approach to evaluate the XPS spectra of the Ti 2p photoemission line in TiN in a self-consistent manner that accounts for all features observable in an energy window of 80 eV. The evaluation considers the appropriate Tougaard background correction, shake-up features as well as surface and bulk plasmons. The ratio of the Ti 2p_1/2 and Ti 2p_3/2 and the corresponding peaks in the energy loss features fulfill the requirements given by quantum mechanics. The energy loss ΔE due to the shake-up process and the shake-up ratio have been determined quantitatively for oxygen-free bulk titanium nitride. The origin of the shake-up, its intensity and energy difference ΔE are explained by a two electron excitation process.     

Characteristic energy loss measurements of slow electrons on clean and adsorbate-covered Ru(001)

Characteristic energy losses of low energy electrons backscattered from Ru(001) have been measured under conditions of very low primary electron currents for the clean and the CO- or oxygen-covered surface. The main losses found for the clean and the CO-covered surface are similar to those observed as XPS core satellites which may mean that the influences of the core hole on the initial and the final states of the valence shake-up are about the same. A peak in the secondary electron spectrum of the clean surface is found at 11 eV which is changed by adsorption. The results are discussed in terms of the excitations of the metal and the adsorbates.     

Evidence for shakeup satellites due to surface contamination in arsenic metal and its compounds

Satellites accompanying the main peaks have been observed in the X-ray photo-electron spectra of arsenic metal and its compounds. These satellites are examined in terms of various mechanisms such as multi-electron excitation energy losses. In addition to plasm on satellites, a satellite doublet associated with the 3d peak is attributed to charge-transfer shakeup from the 2pσ level of carbon (present as a surface contamination) to the Fermi level of arsenic. Such charge-transfer shake-up satellites may be caused by a difference in the relaxation energy of surface arsenic atoms as compared to bulk arsenic atoms resulting from the presence of weakly bonded carbon.     

双电子复合过程的相对论理论研究 通道的变化特性

双电子复合是一种共振辐射复合过程,在这一过程中,一个具有特定能量的自由电子与电离度为q的离子A~(+q)碰撞,形成有两个电子激发的自电离态n_(?)l_(?)nl,该自电离态进一步发射光子,复合成A~(+(q-1))离子,一系列n(?)l_(?)nl自电离态(n_(?)l_(?)l固定,n从有限到无限变化)形成一个通道,本文在相对论单组态理论基础上,具体探讨了类氦铁离子(3s_(1/2)~nP_(1/2))J=(?)通道中,双电子复合速率随n的变化规律,根据本文得到的规律,可以很方便地计算任意离子的任意一 关键词：     

Satellites in ESCA inner-shell spectra of 3d0 transition metal complexes

The occurrence of satellites to inner shell ESCA spectral lines is discussed for ions in the beginning of the transition metal series. It is found that the satellites correspond to e′_g → e″_g and t′_2g → t″_2g shake-up transitions, where e″_g and t″ _2g have mainly metal ion 3d-character. The intensity is found to increase with relaxation charge transfer and to decrease with the 3d occupancy in the neutral ground state.     

Electron-induced KLL Auger electron spectroscopy of Fe,Cu and Ge

KLL Auger spectra excited by electrons with energies in the 30–35 keV range of Fe, Cu and Ge films were measured, using thin free-standing films. It was possible to obtain spectra with an energy resolution of about 1 eV. The observed spectra can not be described satisfactorily by just the multiplet splitting of the final state as calculated for an isolated atom. Additional features, due in part to intrinsic (shake satellites) and in part to extrinsic (energy loss of the escaping electron) processes formed a large fraction on the observed intensities. In particular a number of distinct satellite structures that are not predicted by the atomic Auger process are observed. For Fe and Cu the satellite peaks can be explained in terms of shake-up processes from the 3d_5/2–4d_5/2 states. Similar satellite structures observed in Ge are partly attributed to plasmon creation and partly to shake-up processes. It is demonstrated that both the thickness dependence of the observed intensity distributions and transmission electron energy loss measurements contain invaluable information for the interpretation of these spectra.     

X-ray photoelectron spectra of cobalt compounds

The X-ray photoelectron spectra of a variety of cobalt(II) and cobalt(III) complexes have been investigated. Intense satellite lines were observed for the 2p, 3s and 3p peaks in the case of the high spin cobalt(II) compounds, but not for low spin cobalt(III) complexes. The satellites of the 2p levels are best explained as arising from shake-up processes, whereas those of the 3s and 3p levels are thought to arise largely from multiplet (exchange) splitting of the levels. Multiplet splitting of the 2p level is small and responsible for an increase in the doublet separation of the 2p_1/2, 2p_3/2 spin-orbit levels of the high spin cobalt(II) compounds. The chemical shifts for cobalt differ for the 2p, 3s and 3p levels of the high spin cobalt(II) compounds. Those of the 2p and 3p levels of diamagnetic cobalt(III) and low spin cobalt(II) complexes are equal. The difference in the case of the high spin cobalt(II) compounds is thought to be due to the presence of unpaired 3d electrons.     

Line emission and alignment effects in state selective electron transfer in He2+-Li(2s, 2pΣ, 2pΠ) collisions

Classical Trajectory Monte-Carlo (CTMC) method has been used to investigate state selective electron capture by He²⁺ ions colliding with Li(2s) and Li(2p) in as well as alignments in the energy range 1-15 keV/amu. He⁺(4l) electron capture, line emission [He II(n = 4 3)] cross-sections and alignment parameters have been calculated and analyzed in the light of the available results. The undulatory structure of the capture and emission cross-sections have been explained qualitatively in terms of a quasi-molecular ion formation. Projectile impact energy and spatial overlap play crucial role in determining the alignment effects. Received 3 July 1998 and Received in final form 3 June 1999     

Multiple-ionization satellites in the L 2, 3 Auger spectra of argon-like molecules

L _{2, 3} Auger spectra of all argon-like molecules (HCl, H₂S, PH₃, SiH₄) have been calculated with inclusion of the multiple ionization satellites. The Auger transition probabilities were calculated with inclusion of the ligand electron density, multiplet splitting, final-state configuration interaction, and spin-orbit splitting of the initial 2p level. The theoretical integrated intensities of the shake-off and shake-up satellites (“with a spectator”) in the L _{2, 3} Auger spectra of argon-like molecules make up 8.2–10.4% of the total Auger spectrum intensity.     

The observation of “forbidden” transitions in He II photoelectron spectra

Anomalous bands are reported in the He II spectra of diatomic and triatomic molecules which are attributed to excitation of a second electron along with the primary ionization. This dual process is made possible by the mixing of ionized states of the same symmetry but different configurations i.e. by configuration interaction between ionized states. The close relationship between the observed bands and those reported in X-ray spectra which result from the so-called shake-up process is discussed.     

Classical trajectory study of alignment effects in the capture process: He2+-Li1(2pΣ,2pΠ) collisions

A simulation method (CTMC) has been used to investigate the selectivity and alignment effects on the capture process in He²⁺-Li¹(2pΣ,2pΠ) collisions. The anomalous results of the experiment (∼ 50% error) as well as the AO calculation of Gieler et al. in case of capture into He II (n = 4) from the initial Li¹ (2pΣ) state are not found in the present work. Relative velocity and spatial overlap together mainly control the capture process in ion-atom collisions. The n-distribution of the final capture state is also presented.     

Chemisorption of CO on Cu(100), Ag(110) and Au(110)

The adsorption of CO on Cu, Ag and Au is studied using core and valence photoemission, X-ray absorption and autoionization of core excited states. The purpose is to investigate the nature of the adsorption bond starting out from the well-established chemisorption system CO/Cu(100)-c(2 × 2), and from the results we suggest that CO forms chemisorbed phases also on Ag(110) and Au(110). The photoemission spectra show strong shake-up satellites both for the valence levels and the core levels. The separation to the satellite appearing closest to the main line is observed to follow the position of the substrate d-band relative to the Fermi level. The CO adsorption strength for the noble metals is deduced to decrease in the order Cu-Au-Ag. This is based on the widths of the XA resonances, which are related to the adsorbate-substrate interaction strength of the core excited states, and the relative shake-up intensities, which are expected to increase with a decreasing adsorption strength in the ground state. The same trends regarding the shake-up intensities are observed both for the valence and core levels.     

L—shell absorption measurement and simulation of x—ray—heated constrained material

Using the newly-designed multi-layered target, we obtain a homogeneous Al sample plasma at high density, low electron temperature, and in near local thermodynamic equilibrium. L-shell resonance absorption lines of Li-like and Be-like ions, as well as satellites are clearly observed. Transition arrays such as 2s－3p, 2s²－2s3p and 2s2p－2p3p are identified. We present the calculation method based on the unresolved transition array model, and we compare the measured transmission spectrum with the calculated results. The electron temperature of the constrained sample plasma is determined to be 34eV with a variation of ±2eV.     

氖等电子序列2p^5nl（l=s,d）系列的高激发态结构

本文用本征通道量子亏损理论方法（ＥＱＤＴ方法）计算了氖等电子序列２ｐ＾５ｎｌ（ｌ＝ｓ，ｄ）系列的高激发态结构。得到基本结构参量（ＥＱＤＴ参量）随净电荷数Ｚｃ增大的变化规律，并从静电相互作用下自旋－轨道相互作用之间的竞争角度给出确切的物理解释。以ＮｅＩ为实例，给出其高激发态结构的具体数值结果。     

The electronic structures of the core and valence ion states of metal oxides

SCF-Xα SW MO calculations on metal core ion hole states and X-ray emission (XES) and X-ray photoelectron (XPS) transition states of the non- transition metal oxidic clusters MgO₆^10?, AlO₄^5? and SiO₄^4? show relative valence orbital energies to be virtually unaffected by the creation of valence orbital or metal core orbital holes. Accordingly, valence orbital energies derived from XPS and XES are directly comparable and may be correlated to generate empirical MO diagrams. In addition, charge relaxation about the metal core hole is small and valence orbital compositions are little changed in the core hole state. On the other hand, for the transition metal oxidic clusters FeO₆^10?, CrO₆^9? and TiO₆^8? relative valence orbital energies are sharply changed by a metal core orbital or crystal field orbital hole, the energy lowering of an orbital increasing with its degree of metal character. Consequently O 2p nonbonding → M 3d-O 2p antibonding (crystal field) energies are reduced, while M 3d bonding → O 2p nonbonding and M 3d-O 2p antibonding → M 4s,p-O 2p antibonding (conduction band) energies increase. Charge relaxation about the core hole is virtually complete in the transition metal oxides and substantial changes are observed in the composition of those valence orbitals with appreciable M 3d character. This change in composition is greater for e _g than for t_2g orbitals and increases as the separation of the e_g crystal field (CF) orbitals and the O 2p nonbonding orbital set decreases. Based on the hole state MO diagrams the higher energy XPS satellite in TiO₂ (at about 13 eV) is assigned to a valence → conduction band transition. The UV PES satellites at 8.2 eV in Cr₂O₃ and 9.3 eV in FeO are tentatively assigned to similar transitions to conduction band orbitals, although the closeness in energy of the crystal field and O 2p nonbonding orbitals in the valence orbital hole state prevents a definite assignment on energy criteria alone. However the calculations do clearly show that charge transfer transitions of the e_g bonding → e_g crystal field orbital type would generally occur at lower energy than is consistent with observed satellite structure.A core electron hole has little effect upon relative orbital energies and is only slightly neutralized by valence electron redistribution for MgO and SiO₂. For the transition metal oxides a core hole lowers the relative energies of M3d containing orbitals by large amounts, reducing O → M charge transfer and increasing M 3d crystal field → conduction band energies. Large and sometimes overcomplete neutralization of the core hole is observed, increasing from CrO₆^9? to FeO₆^10? to TiO₆^8?. as the O → M charge transfer energy declines.High energy XPS satellites in TiO₂ may be assigned to O 2p nonbonding → conduction band transitions while lower energy UV PES satellites in FeO and Cr₂O₃ arise from crystal field or O 2p nonbonding → conduction band excitations. Our “shake-up” assignment for FeO₆^10?, CrO₆^9? and TiO₆^8? are less than definitive because no procedure has yet been developed to calculate “shake-up” intensities resulting from transitions of the type described. However the results do allow a critical evaluation of earlier qualitative predictions of core and valence hole effects. First, we find that the comparison of hole or valence state ionic systems with equilibrium distance systems of higher nuclear and/or cation charge (e.g. the comparison of the FeO₆^10? Fe 2p core hole state to Co₃O₄) is dangerous. For example, larger MO distances in the ion states substantially reduce crystal field splittings. Second, core and CF orbital holes sharply reduce O → M charge transfer energies, giving 2e_g → 3e_g energy separations which are generally too small to match observed satellite energies. Third, highest occupied CF-conduction band energies are only about 4–5 eV in the ground states, but increase to about 7–11 eV in the core and valence hole states of the transition metal oxides studied. The energetic arguments presented thus support the idea of CF and/or O 2p nonbonding → conduction band excitations as assignments for “shake-up” satellites, at least in oxides of metals near the beginning of the transition series.     

Interpretation of Auger satellites in Co,Ni, and Cu compounds

X-ray photoelectron spectra of the 2p levels of Co, Ni, and Cu compounds are examined concurrently with their L₃M_4,5M_4,5 Auger spectra. A correlation is established between the presence or absence of Auger satellites with the presence or absence of photoelectron shake-up satellites for Co and Ni compounds. The correlation is less clear for cupric compounds. We propose the mechanism of Auger shake-up as a plausible interpretation for the observed behavior of these Auger satellites.     

高离化类Ne铕离子的双电子伴线结构的理论研究

在对高离化态类Ne铕离子及其临近的类Na、类Mg离子的n=3→2跃迁的波长和强度详细计算的基础上，考虑了等离子体中单个谱线的展宽和谱线之间的重叠，得到了类Ne铕离子n=3→2的共振线及其类Na和类Mg离子双电子伴线的结构，并系统地分析了这些伴线对共振线波长和强度的影响.