Density functional theory of transition metal phthalocyanines,I: electronic structure of NiPc and CoPc—self-interaction effects

We present a two-part systematic density functional theory study of the electronic structure of selected transition metal phthalocyanines. We use a semi-local generalized gradient approximation (GGA) functional, as well as several hybrid exchange-correlation functionals, and compare the results to experimental photoemission data. Here, we study the low-spin systems NiPc and CoPc. We show that hybrid functionals provide computed photoemission spectra in excellent agreement with experimental data, whereas the GGA functional fails qualitatively. This failure is primarily because of under-binding of localized orbitals due to self-interaction errors.     

Effects of configuration-dependent hybridization on core-level photoemission spectra

The Ni2p X-ray photoemission spectrum (XPS) for NiCl₂ is reanalyzed on the basis of a NiCl₆⁴⁻ cluster model. By taking into account the electron configuration dependence of the hybridization strengths between Ni3d and Cl3p orbitals, we show that the model can consistently reproduce the experimental 2p-XPS and the energy gap of the system.     

Angle-resolved photoemission of chain-like molecules: the electronic band structure of sexithiophene and sexiphenyl

Here we report the electronic π-band structure of sexithiophene obtained from 6T(010) oriented films. The angle-resolved valence band photoemission results taken parallel and perpendicular to the molecular axis are compared to those of sexiphenyl and interpreted in terms of intra- and inter-molecular band dispersion. We show that the strong photoemission intensity variations with emission angle parallel to the molecular axis are well reproduced by the Fourier transforms of the molecular orbitals of the isolated molecules. These results imply that ARUPS can yield quite detailed information about molecular geometry, both in terms of molecular orientation and internal structure.     

Electronic structure and photoemission on VNi3

The electronic structure of VNi₃ has been calculated and compared with the experimental results from photoemission, magnetic susceptibility and heat capacity measurements. The linearized muffintin orbitals method is used to compute the electronic density of states. Both paramagnetic and spin-polarized calculations have been performed and give results in good overall agreement with the experimental data.     

Theory of angle-resolved X-ray photoemission compared with exafs

Angle-resolved photoemission from deep core orbitals on irradiation with soft X-rays is theoretically considered and compared with EXAFS results. Numerical calculations are carried out for ionization from the 1s orbital of O adsorbed on an Al (110) surface, and the results show that the variations of the differential photoionization cross-section in special directions are rapid in comparison with that given by EXAFS with respect to final kinetic-energy variation.     

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.     

Two Gaps in Semiconducting EuSbTe_3 Studied by Angle-Resolved Photoemission Spectroscopy

Using angle-resolved photoemission spectroscopy, we study the low-energy electronic structure of a layered ternary telluride EuSbTe_3 semiconductor. It is found that the photoemission constant energy contours can be well described by the simple two-parameter(t_(perp) and t_(para)) tight-binding model based on the Te orbitals in square-net planes of EuSbTe_3, suggesting its Te 5p orbitals dominated low-lying electronic structure, which is reminiscent of other rare-earth tritellurides. However, a possible charge-density-wave gap of 80 meV is found to persist in 300 K,which renders the unexpected semiconducting properties in EuSbTe_3. Moreover, we reveal an extra band gap occurring around 200 meV below the Fermi level at low temperatures, which can be attributed to the interaction between the main and folded bands due to lattice scatterings. Our findings provide the first comprehensive understanding of the electronic structure of layered ternary tellurides, which lays the basis for future research on these compounds.     

Self-consistent LCGO calculation of positron annihilation in copper

Two-photon momentum density and angular correlation of positron annihilation radiation have been calculated using self-consistent, linear combination of gaussian orbitals band structure method within the independent particle approximation. The resulting anisotropies show very good agreement with the experimental ones.     

Imaging delocalized electron clouds: photoionization of C(60) in Fourier reciprocal space

The dynamics of the photoionization of the two outermost orbitals of C(60) has been studied in the oscillatory regime from threshold to the carbon K edge. We show that geometrical properties of the fullerene electronic hull, such as its diameter and thickness, are contained in the partial photoionization cross sections by examining ratios of partial cross sections as a function of the photon wave number in the Fourier conjugated space. Evaluated in this unconventional manner photoemission data reveal directly the desired spatial information.     

Bonding of nitrogen atoms on Cu(001) surfaces: A cluster approach

A study of the chemisorption of nitrogen atoms on a copper surface has been performed, based on an analysis of the electronic structure of the Cu₅N cluster obtained from self-consistent-field Xα scattered-wave calculations. Our calculations show that the chemisorption of nitrogen on Cu(001) surfaces induces peaks below and above the Cu d-band region in the total density of states curve. The bonding orbitals formed between the N 2p and the Cu valence orbitals are generally found near the bottom of the Cu d-band region, while the antibonding orbitals formed between the N 2p and Cu orbitals are found to lie above the Cu d-band region. These hybridized orbitals involving the N 2p orbital gave a satisfactory interpretation of the adsorbate-induced structure reported in N/Cu(001) ultraviolet photoemission (UPS) studies. In addition, the separate contributions of the N 2p⊥ and 2p∥ states to the total density of states curve of the Cu₅N cluster are given. This information may be useful in interpreting angleresolved UPS data.     

Alkali metal-induced Si(1 1 1) structure: The Na case

We report the first scanning tunneling microscopy (STM) and core-level photoemission (CL-PES) studies of a structure induced by sub-monolayer Na deposition on the Si(1 1 1) surface. In the filled-state STM images, five bright protrusions in the unit cell are located on the Ag trimers of the structure. The Si 2p core-level photoemission decomposition shows that the surface-shifted component originated from the Si-trimer atoms in the surface splits into two for the structure, which are attributed to the Si-trimer atoms in the unit cell which are affected and unaffected by the Na adsorption. These results show strong similarities between the Na-induced superstructure and the noble metal-induced ones, indicating a common atomic structure and formation mechanism.     

Electronic structure and spectra of CuO

We report the electronic structure of monoclinic CuO as obtained from first principles calculations utilizing density functional theory plus effective Coulomb interaction (DFT + U) method. In contrast to standard DFT calculations taking into account electronic correlations in DFT + U gave antiferromagnetic insulator with energy gap and magnetic moment values in good agreement with experimental data. The electronic states around the Fermi level are formed by partially filled Cu 3d _x²?y² orbitals with significant admixture of O 2p states. Theoretical spectra are calculated using DFT + U electronic structure method and their comparison with experimental photoemission and optical spectra show very good agreement.     

Cyanogen on Ni(110): an experimental and theoretical study

Adsorption of cyanogen, C₂N₂, on a Ni(110) surface has been investigated by combining low energy electron diffraction, thermal desorption and angular resolved ultra-violet photoemission experiments as well as model cluster calculations using the linear combination of Gaussian-type orbitals local density functional method as well as a force field approach. Results of mirror plane photoemission experiments on the ordered c(2 × 2) monolayer could be rationalized by invoking adsorbates bonded to the surface via the π electrons, with their axis oriented along the [001] direction, across the grooves of the (110) surface, leading to an assignment of all six adsorbate-derived valence orbitals. However, unlike in a previous study on the analogous chemisorption system Pd(110)/C₂N₂, only one mirror plane was detected. A possible tilt of the adsorbates in the (1 0) plane was related to crowding on the closer spaced nickel surface by estimating the lateral interaction within the adsorption layer using force field models. Electronic structure calculations on various chemisorption model clusters confirmed the experimental orbital assignment and the orientation of the adsorbate axis essentially along the [001] direction. Best agreement with UPS data was found for the orbital splitting pattern of an adsorption geometry where the C-N groups bind sideways on-top of nickel atoms in the first crystal plane. On the other hand, bonding along in the troughs of the (110) surface leads to a distinctly different ordering of the valence orbitals, at variance with the experimental assignment.     

负电子亲和势GaAs光电阴极中的三光子激发和发射的理论研究

将三阶微扰理论应用于单晶GaAs半导体,结合与实际相接近的能带结构,得到了GaAs中三光子吸收系数的解析式表达式,在考虑了激发电子的逃逸过程的情况下,进而推导了负电子亲和势GaAs光电阴极中三光子光电发射的发射系数的解析表达式.两表达式得到的理论数值分别与用ns量级脉宽、2.06μm波长的激光测得的GaAs中三光子吸收系数和GaAs(Cs,O)光电阴极中三光子发射系数的实验值相比较,吻合较好.     

Density of states,charge densities and autocorrelation function of the electronic ground state in orthorhombic sulfur

The molecular orbitals of the S₈ molecule have been calculated selfconsistently without any fitting parameters using the LCAO-MO-method in the STO-4G basis. The ground state charge density, energy spectrum and autocorrelation function of the one-electron density matrix (Fourier transformed Compton profile) are presented and compared with experimental data obtained from the orthorhombic crystal. While the energy spectrum agrees with photoemission data the autocorrelation function shows a strong anisotropy between directions parallel and perpendicular to the plane of the ring. This anisotropy is interpreted in terms of intra- and intermolecular interactions.     

Electronic band structure of Cu3Au: An angle-resolved photoemission study along the [111]-direction

High-resolution normal photoemission (ARPE) spectra have been recorded for Cu₃Au(111) with the use of polarized synchrotron and rare-gas resonance radiation in the photon energy range from 9 to 27 eV. It is for the first time that dispersions of the gold-like bands have been found experimentally. Using a fully relativistic layer-KKR photoemission formalism, occupied and unoccupied bands as well as one-step-model photoemission spectra have been calculated. The comparison of calculated spectra with experimental ones and the observation of direct-transition resonances upon photon energy near the Brillouin zone-center reveal a shift of the unoccupied ground-state bands by about +2.5 eV (self-energy shift). The direct-transition structures in the experimental spectra have been exploited to determine the dispersions of the occupied bands along the [111] direction (A line in k space). In order to determine the wave vector of the experimental direct transitions we used as final state that calculated unoccupied band along [111], which also exists in pure copper and gold up to about 20 eV above the Fermi energy (“unfolded” band structure), shifted by + 2.5 eV. The experimental occupied bands with Cu character are in very good agreement with theory after shifting the latter by about 0.3 eV to lower energy, whereas somewhat bigger discrepancies exist for the gold-like bands.     

Adsorption of 2-butyne on Si(0 0 1) at room temperature: A valence band photoemission study

We present an angle resolved ultraviolet photoemission spectroscopy study of the adsorption of 2-butyne (CH₃-CC-CH₃) on Si(0 0 1)-2 × 1 at room temperature. We recorded valence band photoemission spectra for two azimuthal positions of a vicinal silicon surface, where all the rows formed by the surface silicon dimers are parallel. The photoemission symmetry selection rules allow the determination of the orientation of the molecular orbitals. The photoemission signal of the HOMO is enhanced when the electric field is parallel to the dimer rows. This showed that the π orbital left intact after the cyclo-addition reaction of the molecule with one silicon dimer is parallel to the dimer rows. This indicates that each 2-butyne molecule adsorbs on one silicon dimer. In spite of the size of the system and the vicinity of the orbitals, the angle resolved study points out that no dispersion of the electronic bands occurs. Not all the surface dimers are reacted so some disorder still exists on the surface preventing the formation of Bloch states.     

深紫外激光光发射与热发射电子显微镜在热扩散阴极研究中的应用

对热扩散阴极表面微区发射状态进行原位观察和分析一直是热阴极研究的重要课题.本文着重介绍深紫外激光光发射电子/热发射电子显微镜的基本原理及其在热扩散阴极研究中的典型实例.系统配备了高温激活所用的加热装置,样品可被加热至1400℃.系统具有光发射电子、阴极热发射电子、光发射电子和阴极热发射电子联合三种电子成像模式.应用表明,对于热扩散阴极而言,深紫外激光光发射电子像适于呈现阴极表面的微观结构形貌;热发射电子像适于反映阴极表面的本征热电子发射及均匀性;光电子和热电子联合成像适于对阴极表面的有效发射点做出精确定位.     

Quantum mechanical effects in internal photoemission THz detectors

The variation in spectral shape around the threshold frequencies between model and experimental responsivity spectra in heterojunction interfacial workfunction internal photoemission (HEIWIP) infrared detectors was investigated. This is attributed to the loss of photoexcited carriers, within the escape cone, prior to photoemission. The energy dependent transmission of excited carriers is incorporated to the existing photoemission model to show that emission around the threshold frequency is reduced considerably by quantum mechanical reflection of photoexcited carriers as observed in experimental results. In the new model, the photoemission of carriers become bias dependent.     

Charge transfer between isomer domains on n(+)-doped Si(111)-2?×?1: energetic stabilization

Domains of different surface reconstruction-negatively or positively buckled isomers-have been previously observed on highly n-doped Si(111)-2?×?1 surfaces by angle-resolved ultraviolet photoemission spectroscopy and scanning tunneling microscopy/spectroscopy. At low temperature, separate domains of the two isomer types are apparent in the data. It was argued in the previous work that the negative isomers have a lower energy of their empty surface states than the positive isomers, providing a driving force for the formation of the negative isomers. In this work we show that the relative abundance of these two isomers shows considerable variation from sample to sample, and it is argued that the size of the isomer domains is likely to be related to this variation. A model is introduced in which the electrostatic effect of charge transfer between the domains is computed, yielding total energy differences between the two types of isomer. It is found that the transfer of electrons from domains of positive isomers to negative ones leads to an energetic stabilization of the negative isomers. The model predicts a dependence of the isomer populations on doping that is in agreement with most experimental results. Furthermore, it accounts, at least qualitatively, for the marked lineshape variation from sample to sample observed in photoemission spectra.