Experimental and Theoretical Electronic Structure Investigations on alpha-Nb(3)Cl(8) and the Intercalated Phase beta'-NaNb(3)Cl(8)

The electronic structures of the cluster compound alpha-Nb(3)Cl(8) and the intercalated phase beta'-NaNb(3)Cl(8) have been studied by core level and valence band X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS), diffuse reflectance spectroscopy, and charge-self-consistent molecular orbital (CSC-EH) and band structure (CSC-EH-TB) calculations. The crystal structures of the two compounds consist of layers of interconnected Nb(3)Cl(13) units. XP and UP valence band spectra as well as the band structure calculations show well separated sets of Cl 3p levels at lower energy (higher binding energy) and Nb 4d levels at higher energy (lower binding energy), indicative of mainly ionic Nb-Cl bonding. The UP spectra of alpha-Nb(3)Cl(8) reveal a triple-peak structure for the Nb 4d levels, corresponding to the 1a(1), 1e, and 2a(1) metal-metal bonding orbitals of a seven-electron Nb(3) cluster as suggested by theory. The valence band shapes are in good agreement with the theoretical density-of-states curve. The relative intensities in the XP valence band spectra of beta'-NaNb(3)Cl(8) evidence an additional electron in the Nb 4d orbitals. The better resolved UP spectra, however, show a broad pattern for the Nb 4d levels which is neither expected from a single cluster model nor given by the theoretical density-of-states curve. Possible origins for this discrepancy between experiment and theory are discussed. Electrostatic interactions between Na(+) and Cl(-) ions in beta'-NaNb(3)Cl(8) lead to a narrowing of the Cl 2p core level and Cl 3p valence band signals, the former being shifted to higher binding energy in comparison to alpha-Nb(3)Cl(8). Two rather narrow absorptions in the optical spectra of alpha-Nb(3)Cl(8) are assigned to the transitions from the 1a(1) and 1e levels into the singly occupied 2a(1) orbital. These absorptions are missing in the optical spectra of beta'-NaNb(3)Cl(8), in agreement with the theoretical expectations for an eight electron Nb(3) cluster.     

The X-ray photoelectron spectra of MnS,MnSe, and MnTe

The core level binding energies and valence band spectra of MnS, MnSe, and MnTe have been examined by X-ray photoelectron spectroscopy. The results demonstrate that the compounds are substantially more ionic in character than related transition metal compounds, and that the compounds lack significant metalmetal interactions, accounting for the nontypical nature of the compounds as transition metal chalcides.     

Photoelectron spectra of some antibiotic building blocks: 2-azetidinone and thiazolidine-carboxylic Acid

X-ray photoelectron spectra of the core and valence levels of the fundamental building blocks of β-lactam antibiotics have been investigated and compared with theoretical calculations. The spectra of the compounds 2-azetidinone and the 2- and 4-isomers of thiazolidine-carboxylic acid are interpreted in the light of theoretical calculations. The spectra of the two isomers of thiazolidine-carboxylic acid are rather similar, as expected, but show clear effects due to isomerization. Both isomers are analogues of proline, which is well-known to populate several low energy conformers in the gas phase. We have investigated the low energy conformers of thiazolidine-4-carboxylic acid theoretically in more detail and find some spectroscopic evidence that multiple conformers may be present. The measured valence levels are assigned for all three compounds, and the character of the frontier orbitals is identified and analyzed.     

Correlation of electronic structures of three cyclic dipeptides with their photoemission spectra

We have investigated the electronic structure of three cyclic dipeptides: cyclo(Glycyl-Glycyl) (cGG), cyclo(Leucyl-Prolyl) (cLP), and cyclo(Phenylalanyl-Prolyl) (cPP). These compounds are biologically active and cLP and cPP are derived from cGG (also known as diketopiperazine), by the addition of the respective functional groups of the amino acids, namely, phenyl, alkyl or a fused pyrrolidine ring (proline). Experimental valence and core level spectra have been interpreted in the light of theoretical calculations to identify the basic chemical properties associated with the central ring, and with the additional functional groups in cLP and cPP. The theoretically simulated spectra of all three cyclic dipeptides in both valence and core spaces agreed reasonably well with the experimental spectra. The three molecules displayed similarities in their core spectra, suggesting that the diketopiperazine structure plays an important role in determining the inner shell spectrum. The experimental C 1s spectra of cLP and cPP are analogous but differ from cGG due to the side chains attached to the diketopiperazine structure. Single spectral peaks in the N 1s (and O 1s) spectra of the dipeptides indicate that the chemical environment of the nitrogen atoms (and oxygen atoms) are very similar, although they show a small splitting in the simulated spectra of cPL and cPP, due to the reduction of their point group symmetry. Valence band spectra of the three dipeptides in the frontier orbital region of 9-11 eV exhibit similarities; however theoretical analysis shows that significant changes occur due to the involvement of the side chain in the frontier orbitals of cPP, while lesser changes are found for cLP.     

Fingerprints of the hydrogen bond in the photoemission spectra of croconic acid condensed phase: an x-ray photoelectron spectroscopy and ab-initio study

The electronic structure of Croconic Acid in the condensed phase has been studied by comparing core level and valence band x-ray photoelectron spectroscopy experiments and first principles density functional theory calculations using the Heyd-Scuseria-Ernzerhof screened hybrid functional and the GW approximation. By exploring the photoemission spectra for different deposition thicknesses, we show how the formation of the hydrogen bond network modifies the O 1s core level lineshape. Moreover, the valence band can be explained only if the intermolecular interactions are taken into account in the theoretical approach.     

Optical absorption and valence band photoemission from uncapped CdTe nanocrystals

CdTe nanocrystals have been successfully fabricated by a mechanical alloying process. X-ray diffraction (XRD) patterns demonstrate that a single-phase CdTe compound with a zinc blende structure has been formed after ball milling elemental Cd and Te mixture powders for 27 h. The large broadening effect for the width of the {111} diffraction peak of uncapped CdTe nanocrystals on smaller size was observed in slowly scanned XRD patterns. The X-ray photoelectron spectrum was used to study the surface of the uncapped CdTe nanocrystals within both core level and valence band regions. The presence of tellurium oxide film on the surface of the uncapped CdTe nanocrystals has been detected in the X-ray photoelectron spectrum of the Te 3d core level, which was comparable to the observed amorphous oxide thin layer on the surface of uncapped CdTe nanocrystals in a high resolution transmission electron microscopy (HRTEM) image. The energy of the valence band maximum for uncapped CdTe powders blue shifts to the higher energy side with smaller particle sizes. In UV-visible optical absorption spectra of the suspension solution containing uncapped CdTe nanocrystals, the absorption peaks were locating within the ultraviolet region, which shifted toward the higher energy side with prolonged ball milling time. Both blue shifts of valence band maximum energy and absorption peaks with decreasing particle size provide a unique pathway to reveal the quantum confinement effect of uncapped CdTe nanocrystals.     

Photoelectron spectra and structures of three cyclic dipeptides: PhePhe, TyrPro, and HisGly

We have investigated the electronic structure of three cyclic dipeptides: cyclo(Histidyl-Glycyl) (cHisGly), cyclo(Tyrosyl-Prolyl) (cTyrPro), and cyclo(Phenylalanyl-Phenylalanyl) (cPhePhe) in the vapor phase, by means of photoemission spectroscopy and theoretical modeling. The last compound was evaporated from the solid linear dipeptide, but cyclised, losing water to form cPhePhe in the gas phase. The results are compared with our previous studies of three other cyclopeptides. Experimental valence and core level spectra have been interpreted in the light of calculations to identify the basic chemical properties associated with the central diketopiperazine ring, and with the additional functional groups. The valence spectra are generally characterized by a restricted set of outer valence orbitals separated by a gap from most other valence orbitals. The theoretically simulated core and valence spectra of all three cyclic dipeptides agree reasonably well with the experimental spectra. The central ring and the side chains act as independent chromophores whose spectra do not influence one another, except for prolyl dipeptides, where the pyrrole ring is fused with the central ring. In this case, significant changes in the valence and core level spectra were observed, and explained by stronger hybridization of the valence orbitals.     

Study of electron states of solids by techniques of electron spectroscopy

Studies of valence bands and core levels of solids by photoelectron spectroscopy are described at length. Satellite phenomena in the core level spectra have been discussed in some detail and it has been pointed out that the intensity of satellites appearing next to metal and ligand core levels critically depends on the metal-ligand overlap. Use of photoelectron spectroscopy in investigating metal-insulator transitions and spin-state transitions in solids is examined. It is shown that relative intensities of metal Auger lines in transition metal oxides and other systems provide valuable information on the valence bands. Occurrence of interatomic Auger transitions in competition with intraatomic transitions is discussed. Applications of electron energy loss spectroscopy and other techniques of electron spectroscopy in the study of gas-solid interactions are briefly presented.     

Soft-x-ray photoemission spectroscopy and ab initio studies on the adsorption of NO2 molecules on defective multiwalled carbon nanotubes

The adsorption of NO(2) molecules on defective multiwalled carbon nanotubes has been studied by soft-x-ray photoemission. The valence band and carbon core-level spectra have been acquired before, during, and after NO(2) exposure. The spectra show a reversible decrease of the density of states at the top of the valence band when NO(2) molecules are adsorbed on the (carbon nanotubes) CNTs. No shift of the C 1s spectra has been observed. Theoretical calculations, using density-functional theory, have been performed on the CNT + NO(2) system, considering semiconducting nanotubes with different diameters and introducing a Stone-Wales [Chem. Phys. Lett. 128, 501 (1986)] defect. The calculation confirms the decrease of the density of states at the top of the valence band in the CNT + NO(2) system, while close to the adsorption site new states appear very close to the Fermi level.     

LnCu_2O_4(Ln=Gd,Nd)电子结构的XPS研究

用 XPS测定了 LnCu2O4(Ln=Gd, Nd)的内层和价层电子能谱,观察到 LnCu2O4中稀土金属的 3d电子结合能比相应的稀土金属简单氧化物的 3d结合能低 0.8～ 0.9 eV,而 Cu的 2p电子结合能比 CuO的高 0.4～ 0.5 eV,因此推断在 LnCu2O4的 Ln－ O－ Cu链中存在 Cu→ O→ Ln电荷转移 .XPS分析还表明 LnCu2O4的 Cu原子上有较低的电荷密度,但不存在混合价态 .此外,通过比较价电子能谱,发现 NdCu2O4的 Ln 4f Cu 3d O 2p价带中心比 GdCu2O4的价带中心向 Fermi能级移近了 3.4 eV,而且 NdCu2O4的价带谱更窄 .     

Analytical utility of valence band X-ray photoelectron spectroscopy of iron and its oxides,with spectral interpretation by cluster and band structure calculations

The valence band and core-level X-ray photoelectron spectroscopy (XPS) of iron and its oxides are reported, and the valence band spectra interpreted by various calculation models. The paper focuses upon the valence band region, which shows significant differences between the metal and the following oxidized iron species: FeO, Fe(3)O(4), alpha-Fe(2)O(3), gamma-Fe(2)O(3), alpha-FeOOH and gamma-FeOOH. The core region is of little analytical value as a means of distinguishing between these species, but the valence band region shows significant differences. These differences are consistent with spectra predicted by cluster and band structure calculations. Cluster calculations are valuable as a means for interpreting the spectra of iron oxides with multiple iron sites and defect characteristics.     

Photoemission on gold-55-clusters derived from gold-phosphine AuP(C6H5)3Cl

We measured XPS and UPS spectra of gold clusters with 55 atoms, embedded in an electrically isolating phosphine matrix, and of gold-phosphine, from which the clusters were chemically derived. Compared to the spectra of bulk gold the valence band spectrum and the core level spectra of the clusters showed shifts of the peaks and the fermi level to higher binding energies. The shift of the peaks could qualitatively be interpreted by a final state effect. We succeeded in a separation of bulk and surface contributions to the core level spectra and in a reasonable quantitative analysis of the valence band spectrum of the clusters. The Au 4f core level spectrum of gold-phosphine showed two peaks at 1.5 eV higher binding energies than the corresponding peaks of the clusters.     

LnCu2O4(Ln=Gd,Nd)电子结构的XPS研究

用XPS测定了LnCu2O4(Ln=Gd, Nd)的内层和价层电子能谱,观察到LnCu2O4中稀土金属的3d电子结合能比相应的稀土金属简单氧化物的3d结合能低0.8～0.9 eV,而Cu的2p电子结合能比CuO的高0.4～0.5 eV,因此推断在LnCu2O4的Ln－O－Cu链中存在Cu→O→Ln电荷转移.XPS分析还表明LnCu2O4的Cu原子上有较低的电荷密度,但不存在混合价态.此外,通过比较价电子能谱,发现NdCu2O4的Ln 4f Cu 3d O 2p价带中心比GdCu2O4的价带中心向Fermi能级移近了3.4 eV,而且NdCu2O4的价带谱更窄.     

Some theoretical aspects of vibrational fine structure accompanying core ionizations in N2 and CO

Ab initio calculations have been carried out on CO and N₂ and the relevant core hole states with different basis sets to investigate differences in geometries and force constants. From these calculations vibrational band profiles of the core level ESCA spectra for these molecules have been interpreted, obviating the need to rely on data pertaining to the equivalent core species. The agreement with experimental profiles is excellent. The O_1s level of CO which has not been subjected to detailed theoretical analysis previously, is predicted to show substantial vibrational structure in excellent agreement with recently acquired experimental data. The effect of temperature on the band profiles has also been considered. Theoretically derived core binding and relaxation energies of these systems have been investigated both as a function of basis set, and of internuclear distance. Density difference contours have been computed and give a straightforward pictorial representation of the substantial electron reorganizations accompanying core ionizations. Small basis sets with valence exponents appropriate to the equivalent core species when used in hole state calculations describe bond lengths, force constants, core binding energies and relaxation energies with an accuracy comparable to that appropriate to the corresponding extended basis set calculations.     

Photoelectron spectroscopic studies of the formation of hydroxyapatite films on 316L stainless steel pretreated with etidronic acid

The valence band and core‐level X‐ray photoelectron spectroscopy was used to probe hydroxyapatite films formed on the surface of stainless steel. These films formed on steel may find application in medical implants. The key to the successful adhesion of the hydroxyapatite films is shown to be the initial formation of a thin, oxide‐free etidronate film on the metal. It was not found possible to prepare the hydroxyapatite films directly on the metal surfaces. Since hydroxyapatite is a key component of bone and teeth, it is likely that the coated metals will have desirable biocompatible properties. The hydroxyapatite film was exposed to air, water, and 1M sodium chloride solution as representative components of the environment of the film in the human body, and these exposures led to no detectable decomposition of the film. The thin hydroxyapatite and etidronate film on the metal show differential charging effects that caused a doubling of the peaks in some core level spectra. The valence band spectra proved especially valuable in the identification of the surface chemistry of the films, and these spectra were interpreted by comparing the experimental spectra with spectra calculated using band structure calculations which showed good agreement with experiment. The calculated spectrum of etidronic acid was found to be significantly different to that of etidronate. Copyright © 2012 John Wiley & Sons, Ltd.     

Examination of the bonding in binary transition-metal monophosphides MP (M = Cr, Mn, Fe, Co) by X-ray photoelectron spectroscopy

The binary transition-metal monophosphides CrP, MnP, FeP, and CoP have been studied with X-ray photoelectron spectroscopy. The shifts in phosphorus 2p(3/2) core line binding energies relative to that of elemental phosphorus indicated that the degree of ionicity of the metal-phosphorus bond decreases on progressing from CrP to CoP. The metal 2p(3/2) core line binding energies differ only slightly and show similar line shapes to those of the elemental metals, reaffirming the notion that these transition-metal phosphides have considerable metallic character. The satellite structure observed in the Co 2p(3/2) X-ray photoelectron spectra of Co metal and CoP was examined by reflection electron energy loss spectroscopy and has been attributed to plasmon loss, not final state effects as has been previously suggested. Valence-band spectra of the transition-metal phosphides agree well with the density of states profiles determined from band structure calculations. The electron populations of the different electronic states were extracted from the fitted valence-band spectra, and these confirm the presence of strong M-P and weak P-P bonding interactions. Atomic charges determined from the P 2p core line spectra and the fitted valence-band spectra support the approximate formulation M(1+)P(1-) for these phosphides.     

Xps measurement and molecular orbital calculation of valence band electronic structure of sodium cyanate

The electronic structure of the core and the valence band region of sodium cyanate is investigated by X-ray photoelectron spectroscopy (XPS). The energy levels and the molecular wavefunctions of the NCO^? ion are calculated by the INDO method and the results are used to obtain the photoionization cross sections for the valence levels of the anion. A simulation of the XPS spectra in good agreement with the experimental spectra is obtained.     

Theoretical investigation of excited states of oligothiophene anions

Electron-hole symmetry upon p- and n-doping of conducting organic polymers is rationalized with Hückel theory by the presence of symmetrically located intragap states. Since density functional theory (DFT) predicts very different geometries and energy level diagrams for conjugated pi-systems than semiempirical methods, it is an interesting question whether DFT confirms the existence of electron-hole symmetry predicted at the Hückel level. To answer this question, geometries of oligothiophene anions with 5-19 rings were optimized and their UV/vis spectra were calculated with time-dependent DFT. Although DFT does not produce symmetrically placed sub-band energy levels, spectra of cations and anions are almost identical. The similarity in transition energies and oscillator strengths of anions and cations can be explained by the fact that the single sub-band energy level of cations lies above the valence band by the same amount of energy as the single sub-band level of anions lies below the conduction band. This and the resemblance of the energy level spacings in valence bands of cations to those in conduction bands of anions give rise to peaks with equal energies and oscillator strengths.     

Electronic structure, X-ray absorption, and optical spectroscopy of LaCoO(3) in the ground-state and excited-states

We present the magnetic and optical properties of various combinations of ordered spin state configurations between low-spin (LS) state, intermediate-spin (IS) state, and high-spin (HS) state of LaCoO(3) . In this study, we use the state-of-the-art first principles calculations based on generalized gradient (GGA) + Hubbard U approach. The excited-state properties of different spin configurations of LaCoO(3) such as the X-ray absorption spectra, optical conductivity, reflectivity, and electron energy loss are calculated. We have demonstrated that the optical spectra results can be used for analyzing the spin state of Co(3+) ion. The first specie is the local excitation of IS cobalt ions in the LS ground state. The second excitation leads to the stabilization of the mixed IS/HS Co(3+) metallic state. At low temperature, the comparison between O 2p and Co 3d projected density of states with the experimental valence band spectra indicates significant IS Co(3+) ions and this is in sharp contrast to the HS state which is negligible. The line shape of O 2s and Co 3d core level spectra are well reproduced in this study. The present results are in excellent agreement with the available experimental data. The variation in the spectra of different configurations of LaCoO(3) suggests a changing in the spin state as the temperature is enhanced from 90 to 500 K.     

N doping of TiO2(110): photoemission and density-functional studies

The electronic properties of N-doped rutile TiO2(110) have been investigated using synchrotron-based photoemission and density-functional calculations. The doping via N2+ ion bombardment leads to the implantation of N atoms (approximately 5% saturation concentration) that coexist with O vacancies. Ti 2p core level spectra show the formation of Ti3+ and a second partially reduced Ti species with oxidation states between +4 and +3. The valence region of the TiO(2-x)N(y)(110) systems exhibits a broad peak for Ti3+ near the Fermi level and N-induced features above the O 2p valence band that shift the edge up by approximately 0.5 eV. The magnitude of this shift is consistent with the "redshift" observed in the ultraviolet spectrum of N-doped TiO2. The experimental and theoretical results show the existence of attractive interactions between the dopant and O vacancies. First, the presence of N embedded in the surface layer reduces the formation energy of O vacancies. Second, the existence of O vacancies stabilizes the N impurities with respect to N2(g) formation. When oxygen vacancies and N impurities are together there is an electron transfer from the higher energy 3d band of Ti3+ to the lower energy 2p band of the N(2-) impurities.