The electronic structure of KMnO4 investigated by resonant photoemission

The valence band of potassium permanganate (KMnO₄) was investigated by means of resonant photoemission spectroscopy (ResPES) at the Mn2p, Mn3p and O1s edge. These data confirm the previous conclusions of a strong deviation from a purely ionic charge distribution in this compound. The ResPES data are in agreement with previous results about the character of the individual valence band states. A simple cluster model is used to explain qualitatively the different structures seen in the valence band spectra and their dependence on the photon energy.     

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     

The electronic structure of gold studied by photoemission

Measurements of the photoemission spectra from gold films of different workfunction are reported. Clear evidence is seen for the importance ofk conservation in transitions from the 5d-bands. Comparison with the band structure calculated by Christensen suggests that all the features in the spectrum could be explained by direct transitions.     

Absolute determination of electronic band structure of copper by angle-resolved photoemission

Structures in the angle-resolved photoemission spectra from copper in the (1$\text{1}$0) and (001) mirror planes at fixed photon energy hν as a function of emission angle show discontinuities in energy position or slope as function of emission angle. These discontinuities are due to the appearance of specific interband transitions on zone boundaries. The appearance angle allow the absolute determination of momentum $\text{k}$ of the transition. E($\text{k}$) points have been determined for most d-bands and several conductions bands. Experimental data are in good agreement with Burdick's band calculation, as also are the E($\text{k}$) points which have been determined using the energy coincidence method.     

Heterostructured organic interfaces probed by resonant photoemission

The application of the resonant photoemission spectroscopy (RPES) to various organic molecule based systems is reviewed. The chemical specificity and the possibility to conduct experiments in the energy domain that provides a time scale for charge dynamics, make the RPES a powerful tool to study organic heterojunctions and in particular to probe the charge transfer processes at organic interfaces. We briefly discuss the models used in RPES data analysis to extract the time scale of the excited charge delocalisation and the spatial correlation of core, valence occupied and unoccupied molecular states. As an example we report on 3,4,9,10-perylene tetracarboxylic acid dianhydride (PTCDA) on (1 × 2) Au(1 1 0) surface where organic layer metallicity is directly evidenced in RPES experiments. A particular attention is dedicated to bio-mimetic model molecules whose electronic structure at interfaces is the fundamental key for the design of real devices. In the last section we consider recent experiments that could open the way to new fields of applications regarding biological molecules and single molecule systems where RPES could elucidate the link between the quantum and the meso-scopic properties of such systems.     

Electronic surface states investigated by means of photoemission spectroscopy

Ultraviolet photoemission spectroscopy (UPS) as an investigative method for surface states is presented. The measured energy distribution curve (EDC) furnishes information on the electronic density of states distribution in the valence band, nearest to the core levels and surface states. The measured angle resolved EDC's provide the possibility to determine the energy-momentum E(k) dependence of electrons in the bulk of the crystal and on the surface. Application of the synchrotron-storage ring system as a source of ultraviolet radiation in the energy range from 10 to 300 eV opens new avenues to investigate structure of electronic states. It features the following possibilities: (1) To distinguish the contribution of the surface and bulk states to the obtained EDC by measuring the change of the EDC when varying the exciting energy hv around the minimum of the escape depth (E = 80 eV) and outside of this region. (2) To discriminate in the valence band the contribution of the d-electrons from that of the s-p electrons due to a different change of the photoemission cross section of the d and s-p electrons with a change of hv. (3) To recognize the localized and delocalized contribution to the density of states in the valence band and to determine E(k) for these electrons by measurements of the angle resolved EDC. (4) To obtain information on the initial and final state distribution using the constant initial states (CIS) and/or constant final states (CFS) techniques. The potential of the photoemission technique will be illustrated by the results of the electronic structure investigation of some metals and semiconductors.     

Doping-dependent electronic structure of cuprates studied using angle-scanned photoemission

Full k -maps of the electronic structure near the Fermi level of differently doped cuprates measured with angle-scanned photoelectron spectroscopy are presented. The valence band maximum of the antiferromagnetic insulator Sr₂CuO₂Cl₂, which is taken as a representative of an undoped cuprate, and the Fermi surfaces of overdoped, optimally doped and underdoped Bi₂Sr₂CaCu₂O_8+δ high-temperature superconductors are mapped in the normal state. The results confirm the existence of large Luttinger Fermi surfaces at high doping with a Fermi surface volume proportional to (1+x), where x is the hole concentration. At very low doping, however, we find that this assumption based on Luttinger's theorem is not fulfilled. This implies a change in the topology of the Fermi surface. Furthermore the intensity of the shadow bands observed on the Fermi surface of Bi₂Sr₂CaCu₂O_8+δ as a function of the doping is discussed. Received 12 October 1999 and Received in final form 12 April 2000     

苝四甲酸二酐薄膜电子结构的同步辐射共振光电子能谱研究

利用基于同步辐射的近边X射线吸收精细结构谱(NEXAFS)和共振光电子谱(RPES)研究了苝四甲酸二酐分子(PTCDA)薄膜的电子结构.碳K边NEXAFS谱中能量小于290 eV的四个峰对应于PTCDA分子不同化学环境碳原子1s电子到未占据分子轨道的共振跃迁.RPES谱中观察到共振光电子发射和共振俄歇电子发射导致的共振峰结构,以及二次谐波激发的碳1s信号.根据电子动能对入射光能量的依赖性分别对三类峰结构进行了归属.同时,发现PTCDA分子轨道共振光电子峰的强度具有光子能量依赖性.这种能量选择性共振增强效应是由于PTCDA分子轨道空间分布差异导致的.共振俄歇峰主要源于高结合能(4.1 eV)分子轨道能级电子参与的退激发过程.明确RPES实验谱图中各个峰结构的起源有助于准确利用基于RPES的芯能级空穴时钟谱技术定量估算有机分子/电极异质界面处电子从分子未占据轨道到电极导带的超快转移时间.     

The local electronic structure of tin phthalocyanine studied by resonant soft X-ray emission spectroscopies

The electronic structure of thin films of the organic semiconductor tin phthalocyanine (SnPc) has been investigated by resonant and non-resonant soft X-ray emission (RXES and XES) at the carbon and nitrogen K-edges with excitation energies determined from near edge X-ray absorption fine structure (NEXAFS) spectra. The resultant NEXAFS and RXES spectra measure the unoccupied and occupied C and N 2p projected density of states, respectively. In particular, RXES results in site-specific C 2p and N 2p local partial density of states (LPDOS) being measured. An angular dependence of C 2p and N 2p RXES spectra of SnPc was observed. The observed angular dependence, the measured LPDOS and their correspondence to the results of density functional theory calculations are discussed. Observed differences on the same site-specific features between resonant (non-ionising) and non-resonant (ionising) NXES spectra are attributed to symmetry selection and screening.     

An investigation of the electronic structure of silver azide by the photoemission method

The energy structure of silver azide was investigated by the photoemission method. The photoelectric work function for photons in the energy range 6.7–11.2 eV was determined from the electron energy distribution curves and the Einstein equation. The position of the Fermi level was determined from the difference in stopping potentials for silver metal and silver azide. The position of the acceptor levels is estimated and the structure of the valence band is discussed. A band scheme for silver azide is proposed.     

Anisotropic ultrafast dissociation probed by the Doppler effect in resonant photoemission from CF4

The resonant Auger spectrum from the decay of F 1s-excited CF4 is measured. Several lines exhibit a nondispersive kinetic energy as the exciting photon energy is tuned through the resonance region. The F 1s(-1) atomiclike Auger line is split into two components due to the emission of Auger electrons by a fragment in motion, when electron emission is observed along the polarization vector of the light. This Doppler splitting is direct evidence that the core excitation leads to T(d)-->C(3v) symmetry lowering, by elongation of a specific C-F bond preferentially aligned along the polarization vector of the incident photon.     

Unusual electronic structure of Dirac material BaMnSb_2 revealed by angle-resolved photoemission spectroscopy

High resolution angle resolved photoemission measurements and band structure calculations are carried out to study the electronic structure of BaMnSb_2. All the observed bands are nearly linear that extend to a wide energy range. The measured Fermi surface mainly consists of one hole pocket around Γ and a strong spot at Y which are formed from the crossing points of the linear bands. The measured electronic structure of BaMnSb_2 is unusual and deviates strongly from the band structure calculations. These results will stimulate further efforts to theoretically understand the electronic structure of BaMnSb_2 and search for novel properties in this Dirac material.     

苯并咪唑苝与金属Ag的界面电子结构研究

利用同步辐射光电子能谱实验技术考察了苯并咪唑苝(BZP)和Ag的界面形成过程与电子结构.单层覆盖度以下时，BZP分子与Ag有弱相互作用，在有机分子禁带中出现明显界面反应态，结合能位于0.9eV.单层铺满后，BZP分子呈现三维岛式生长，且与Ag的相互作用逐渐减弱，同时最高占据分子轨道由于终态效应逐渐向高结合能方向位移至体相结合能位置(2.3eV). Ag衬底上BZP分子的生长导致样品表面功函数减小，表明形成了表面偶极势(Δ=0.3eV)，且电子从有机分子向金属Ag偏移.最后，考察了BZP/Ag 关键词： 有机-金属界面 电子结构 光电子能谱 同步辐射     

Magnetic properties of thin epitaxial films investigated by spin-polarized photoemission

The surface sensitivity of the spin-polarized photoemission experiment was exploited to study two-dimensional magnetism. The magnetization of thin films of Fe, Co, and V in the monolayer (ML) range, grown on Cu(001) and Ag(001) single crystals, was measured as a function of perpendicularly applied field and temperature. Bcc Fe films and fcc Fe and Co films exhibit ferromagnetism down to the single monolayer range, while no evidence for ferromagnetism is found for V on Ag(001). All Co films are magnetized in plane and have a Curie temperature far above room temperature. A thickness dependence of the anisotropy and Curie temperature is observed for the two phases of Fe. Remanent magnetization perpendicular to the surface is found at 30 K for fcc Fe films thicker than 2 ML and for bcc Fe between 3 and 4 ML. The magnetic effects caused by coating and by interdiffusion are discussed in the light of measurements of Cu/Fe/Cu sandwiches and of overlayers obtained by simultaneous evaporation of Fe and Cu. The fcc Fe films are shown to be suitable for thermomagnetic writing.     

Electronic structure of bases in DNA duplexes characterized by resonant photoemission spectroscopy near the Fermi level

The electronic structure of bases in DNA duplexes was investigated by resonant photoemission spectroscopy near the Fermi level, in order to specify charge migration mechanisms. We observed a kinetic energy shift of N-KLL Auger electrons and an intensity enhancement of valence electrons on the resonant photoemission spectra for both poly(dG).poly(dC) and poly(dA).poly(dT) DNAs. These directly show the localized unoccupied states of the bases. We conclude that the charge hopping model is pertinent for electric conduction in a DNA duplex, when electrons pass through the unoccupied states.     

Local electronic structure of phosphorus-doped ZnO films investigated by X-ray absorption near-edge spectroscopy

Using X-ray absorption near-edge structure spectroscopy (XANES), we investigate the local electronic structure of phosphorus (P) and its chemical valence in laser-ablated n-type (as-grown), and p-type (annealed) P-doped ZnO thin films. Both the P L ₁- and P L _2,3-edge XANES spectra reveal that the valence state of P is 3− (P³⁻) in the p-type as well as in the n-type P-doped ZnO. However, the peak intensity is stronger in the former than that in the latter, suggesting that P replaces O (O²⁻ sites with the P³⁻) after rapid thermal annealing. The Zn and O K-edges XANES spectra consistently demonstrate that, in the p-type state, P ions substitutionally occupy O sites in the ZnO lattice.     

Covalency in the electronic structure of Fe3O4: An ultraviolet inverse photoemission investigation

The unoccupied electronic structure of an opend-shell transition metal oxide, namely Fe₃O₄, has been addressed by measuring ultraviolet angle-integrated inverse photoemission (IP) spectra acquired in the isochromat mode (hv=10.2-24 eV). Exploitation of photon energy dependence of symmetry-projected IP cross-sections and comparison with the O 1s X-ray absorption spectrum allow us to recognize a strong covalent admixture of Fe [3d; 4 (sp)]-and O (2p)-derived states in this compound.     

Magnetic circular dichroism in lanthanide 4 d-4 f giant resonant photoemission: terbium

Magnetic circular dichroism in lanthanide 4 f photoemission (PE) multiplets was studied across the 4 d-4 f excitation threshold for the example of Tb metal. The combined experimental and theoretical analysis demonstrates that resonant enhancement of the 4 f PE signal and large magnetic contrast in the PE intensity are obtained simultaneously, when the excitation energy is tuned to the absorption-edge maximum for parallel orientation of magnetization and circular-polarization light helicity. Received 23 February 1999