Valence Photoelectron Spectra Research Articles

Electronic states and growth modes of Zn atoms deposited on Cu(111) studied by XPS, UPS and DFT

Electronic states and growth modes of the Zn-deposited Cu(111) surface at 300K were quantitatively studied using core-level and valence photoelectron spectroscopies. Both Cu 2p and Zn 2p core-levels shifted to higher binding energy with increasing the amount of deposited Zn up to multilayer. The origin of the core-level shift of Cu 2p was further investigated by density functional theory calculations; the shift of the Cu 2p peak results from the change in the effective electrostatic potential (initial state effect) caused by the formation of Zn-Cu surface alloy, and the increase of coordination numbers of surface Cu atoms by Zn overlayer. The observed valence photoelectron spectra show the formation of the two atomic-layer Zn-Cu alloy up to the Zn coverage of 1ML, followed by the formation of three-dimensional Zn islands on the alloyed surface at 300K.

Growth of Bi2Se3 topological insulator thin film on Ge(1 1 1) substrate

Atomically smooth, single crystalline Bi2Se3 thin films were grown on a Ge(111) substrate using molecular beam epitaxy. Crystallinities of both the surface and the bulk as well as the stoichiometry of the grown film were characterized by using low-energy electron diffraction, scanning tunneling microscopy, X-ray diffraction, and photoelectron spectroscopies. Hexagonal atomic structures, quintuple layer steps observed in STM images confirmed that the Bi2Se3 film with a (0001) surface was grown. Diffraction peak positions as well as the chemical composition determined from the core-level photoelectron spectra coincide well with those expected for the Bi2Se3 crystal. The surface state with a Dirac cone was observed in the valence photoelectron spectra, which also support that a high-quality Bi2Se3 film was grown on the Ge(111) substrate. The interface between Ge(111) and Bi2Se3(0001) is expected to be abrupt due to the small lattice between them.

Temperature dependence of Yb valence in the sub-surface of YbB12(001)

The typical Kondo insulator, YbB12, is a candidate of topological Kondo insulators. To clarify the surface electronic structure of not only bulk but also surface by photoelectron measurements, we developed a method to obtain a clean surface of YbB12(001) by annealing at 1650 K in an ultra-high vacuum. By surface-sensitive photoelectron measurements, it was known that the surface consists of only B atoms without Yb. In the sub-surface region, Yb atoms exist and the temperature dependence of the valence agrees with those of previous HAXPES results. Here we report the cleaning method to obtain well-defined YbB12(001) surfaces and the temperature-dependent Yb valence obtained from Yb 3d core-level and valence photoelectron spectra.

Electronic structure transformation in small bare Au clusters as seen by x-ray photoelectron spectroscopy

Free bare gold clusters in the size range from few tens to few hundred atoms (≤1 nm dimensions) have been produced in a beam, and the size-dependent development of their full valence band including the 5d and 6s parts has been mapped ‘on the fly’ by synchrotron-based photoelectron spectroscopy. The Au 4f core level has been also probed, and the cluster-specific Au 4f ionization energies have been used to estimate the cluster size. The recorded in the present work valence spectra of the small clusters are compared with the spectra of the large clusters (N ∼ 103) created by us using a magnetron-based gas aggregation source. The comparison shows a substantially narrower 5d valence band and the decrease in its splitting for gold clusters in the size range of few hundred atoms and below. Our DFT calculations involving the pseudopotential method show that the 5d band width of the ground state increases with the cluster size and by the size N = 20 becomes comparable with the experimental width of the valence photoelectron spectrum. Similar to the earlier observations on supported clusters we interpret our experimental and theoretical results as due to the undercoordination of a large fraction of atoms in the clusters with N ∼ 102 and below. The consequences of such electronic structure of small gold clusters are discussed in connection with their specific physical and chemical properties related to nanoplasmonics and nanocatalysis.

X-ray Photoemission Spectra and Electronic Structure of Coumarin and its Derivatives.

The electronic structures of coumarin and three of its derivatives (7-amino-4-methylcoumarin, 7-amino-4-(trifluoro)methylcoumarin, and 4-hydroxycoumarin) have been studied by theoretical calculations, and compared with experimental valence and core photoelectron spectra to benchmark the predicted spectra. The outer valence band spectra of the first three compounds showed good agreement with theoretical calculations for a single isomer, whereas the spectrum of 4-hydroxycoumarin indicated the presence of more than one tautomer, consistent with published results. Calculations of core level spectra of carbon, nitrogen, oxygen, and fluorine of the first three compounds are also in satisfactory agreement with our measurements. The carbon and oxygen 1s spectra of 4-hydroxycoumarin allow us to identify and quantify the populations of the principle tautomers present. The 4-hydroxy enol form is the most stable isomer at 348 K, followed by the diketo form, with 1.3 kJ·mol(-1) lower energy.

Valence Electronic Structure of Aqueous Solutions: Insights from Photoelectron Spectroscopy.

The valence orbital electron binding energies of water and of embedded solutes are crucial quantities for understanding chemical reactions taking place in aqueous solution, including oxidation/reduction, transition-metal coordination, and radiation chemistry. Their experimental determination based on liquid-photoelectron spectroscopy using soft X-rays is described, and we provide an overview of valence photoelectron spectroscopy studies reported to date. We discuss principal experimental aspects and several theoretical approaches to compute the measured binding energies of the least tightly bound molecular orbitals. Solutes studied are presented chronologically, from simple electrolytes, via transition-metal ion solutions and several organic and inorganic molecules, to biologically relevant molecules, including aqueous nucleotides and their components. In addition to the lowest vertical ionization energies, the measured valence photoelectron spectra also provide information on adiabatic ionization energies and reorganization energies for the oxidation (ionization) half-reaction. For solutes with low solubility, resonantly enhanced ionization provides a promising alternative pathway.

DNA lesion can facilitate base ionization: vertical ionization energies of aqueous 8-oxoguanine and its nucleoside and nucleotide.

8-Oxoguanine is one of the key products of indirect radiation damage to DNA by reactive oxygen species. Here, we describe ionization of this damaged nucleobase and the corresponding nucleoside and nucleotide in aqueous phase, modeled by the nonequilibrium polarizable continuum model, establishing their lowest vertical ionization energies of 6.8-7.0 eV. We thus confirm that 8-oxoguanine has even lower ionization energy than the parental guanine, which is the canonical nucleobase with the lowest ionization energy. Therefore, it can act as a trap for the cationic hole formed by ionizing radiation and thus protect DNA from further radiation damage. We also model using time-dependent density functional theory and measure by liquid jet photoelectron spectroscopy the valence photoelectron spectrum of 8-oxoguanine in water. We show that the calculated higher lying ionization states match well the experiment which, however, is not sensitive enough to capture the electron signal corresponding to the lowest ionization process due to the low solubility of 8-oxoguanine in water.

Dynamical photoionization observables of the CS molecule: the role of electron correlation.

Highly correlated calculations are performed on the primary ionic states and the prominent satellite present in the outer valence photoelectron spectrum of carbon monosulfide (CS). Dyson orbitals are coupled to accurate one particle continuum orbitals to provide a correlated description of energy dependent cross sections, asymmetry parameters, branching ratios, and molecular frame photoelectron angular distributions. The comparison with results obtained at the Hartree-Fock and Density Functional Theory level shows the strong sensitivity of these observables to details of the correlation in the bound states. The behaviour of the well characterized satellite state is analyzed in detail, and shows differences from the relevant primary states, revealing the limitations of a simple intensity borrowing mechanism. The results resolve the intensity disagreement with experiment obtained at the level of the sudden approximation.

Valence Shell Photoelectron Spectroscopy of Pyrene and Fluorene: Photon Energy Dependence in the Far-Ultraviolet Region

Inner and outer valence photoelectron spectra (PES) of pyrene and fluorene, two members of the polycyclic aromatic hydrocarbon (PAH) family, were recorded with a high-resolution synchrotron photoelectron spectrometer. Relative photoelectron emission cross sections were measured at photon energies between 15 and 40 eV. Several bands observed in the experimental PES were assigned with the help of OVGF/cc-pVDZ calculations. The first ionization potentials were estimated to be 7.436 ± 0.015 and 7.944 ± 0.055 eV for pyrene and fluorene, respectively. Photoelectron emission cross sections show a clear difference in trend for inner (σ-dominated) and outer (π-dominated) bands. Contrary to the expectation from the trend observed in benzene, the inner bands significantly dominate in the photon energy region from 15 to 27 eV and then are found to contribute uniformly. A pronounced peak in the cross sections is observed at a photon energy of approximately 17 eV for both molecules (irrespective of the difference in symmetry and structure), particularly for the inner valence bands. The feature is observed to be independent of the details of the molecular orbital associated with the outgoing electron. These observations are correlated to a collective excitation in the far-ultraviolet region.

Comment on: “Valence ionization of l-proline amino acid: Experimental and theoretical study” by F. Fathi, H. Farrokhpour, Chem. Phys. Lett. 565 (2013) 102

In the cited work, the authors presented mass spectra, valence photoelectron spectra and calculations of the electronic structure of proline. They claim that several previous photoelectron spectra are invalid because they were influenced by thermal decomposition of the sample. We present photoionization mass spectra of proline as a function of temperature and show that thermal decomposition does not occur in the apparatus and at the temperatures used in our previous work. These spectra are consistent with other published spectra. The conformer populations calculated by these authors, far from contradicting previous interpretations of valence band spectra, are surprisingly consistent with them.

Interference and diffraction in photoelectron spectra

Theoretical calculations are employed to disentangle the effect due to coherent emission from equivalent centres and diffraction from neighbouring inequivalent atoms in core and valence photoelectron spectra. The molecules investigated are mono and disubstituted fluoro and iodo acetylenes, compared to the simple acetylene system. The two effects appear well separated and additive in the core region, with diffraction giving oscillations of smaller amplitude, shorter period, and more strongly damped. Their interplay is more complex in the valence region giving rise to irregular patterns which, although rich in information, are more difficult to analyze. It is shown that the use of an external standard molecule can be profitably used to reveal diffraction patterns in the case where no internal ratio is available.

Photoelectron spectroscopy of brominated derivative of pyrimidine: 2-bromopyrimidine

In this study the brominated derivative of pyrimidine, 2-bromopyrimidine, was investigated by photoelectron spectroscopy. Outer valence photoelectron spectra recorded at 21.22, 45 and 100 eV photon energy for this compound are presented. The recorded spectra have a higher resolution than that previously reported in the literature. The bromine 3d and 3p edge photoelectron spectra have also been recorded in a photon impact experiment at 100 and 225 eV. All measurements were performed using Double Toroidal Coincidence Spectrometer showing its potential as a versatile apparatus for spectroscopic studies.

Size-Dependent Velocity Map Photoelectron Imaging of Nanosized Ammonia Aerosol Particles

The size dependence of the band position, the bandwidth, and the asymmetry parameter in the valence photoelectron spectrum of ammonia clusters and ultrafine ammonia aerosol particles is investigated for aggregates with diameters up to ~7 nm. The neutral aggregates are ionized by single photons at 13.318 eV from a tabletop vacuum ultraviolet laser. The photoelectrons are detected in a velocity map imaging photoelectron spectrometer. The size distributions of the neutral aggregates are determined independently using the Na-doping method. Up to clusters with a few tens of molecules, the first ionization energy (value at band maximum) decreases, the width of the lowest band in the photoelectron spectrum broadens, and the corresponding asymmetry parameter decreases with increasing cluster size. Constant ("plateau") values of these parameters are found for larger aggregates, which might be explained by a predominantly noncrystalline structure of these aggregates with an average coordination similar to that of the liquid. This explanation is in agreement with previous infrared studies and theoretical predictions.

Valence photoelectron spectra of alkali bromides calculated within the propagator theory

The valence ionization spectra covering the binding energy range 0-45 eV of alkali bromide XBr (X = Li, Na, K, Rb) vapors are studied within the framework of the propagator theory. Relativistic Algebraic Diagrammatic Construction calculations have been carried out in order to investigate photoionization processes and to describe molecular electronic structure. Theoretical results are compared with available experimental data.

Valence ionization of l-proline amino acid: Experimental and theoretical study

High resolution valence photoelectron spectrum of l-proline, up to 20eV, was recorded using He-I radiation (21.218eV) as ionization source in the gas phase. The thermal stability of the sample was checked by recording its mass spectrum at different temperatures to select the proper temperature for evaporating the sample without degradation. Symmetry adapted cluster/configuration interaction (SAC–CI) method based on the single and double excitation (SD-R) operators and natural bonding orbital (NBO) calculations were employed to calculate and assign the photoelectron bands of the four most stable conformers of gaseous l-proline, respectively.

A velocity map imaging photoelectron spectrometer for the study of ultrafine aerosols with a table-top VUV laser and Na-doping for particle sizing applied to dimethyl ether condensation

We present a new experimental configuration for the study of size-dependent, angle-resolved photoelectron and photoion spectra of weakly bound ultrafine aerosol particles targeted at particle sizes below ~20 nm. It combines single photon ionization by a tunable, table-top vacuum ultraviolet laser at energies up to 18 eV with velocity map imaging detection and independent size determination of the aerosol particles using the Na-doping method. As an example, the size-dependence of the valence photoelectron spectrum of dimethyl ether clusters and ultrafine aerosols is investigated. Up to a mean particle diameter of ~3-4 nm, the first ionization energy (value at band maximum) decreases systematically (up to ~1 eV) and the corresponding band broadens systematically (up to a factor of ~3) with increasing aggregate size. Plateau values for band positions and bandwidths are reached beyond a diameter of ~3-4 nm. Experimental evidence for the dominance of the fast intermolecular proton transfer over monomer fragmentation reactions upon ionization is presented via photoion imaging.

Valence electronic structure and photofragmentation of 1,1,1,2-tetrafluoroethane (CF3-CH2F)

The electronic structure and fragmentation of the hydrofluorocarbon compound 1,1,1,2-tetrafluoroethane (CF3-CH2F) were studied using spectroscopical methods and quantum chemical calculations. Valence photoelectron spectra and the ionic fragmentation products were recorded with synchrotron radiation in the vacuum ultraviolet (VUV) region. The geometric and electronic structures of the CF3-CH2F molecule were calculated using the complete active space perturbation theory of second order. The calculated vertical ionization energies were used to interpret the experimental photoelectron spectrum. VUV photodissociation of the sample molecule was studied with photoelectron-photoion coincidence spectroscopy. Coincident ion yields are shown for several cations as a function of electron binding energy. The experimental data are discussed in comparison with theory and previous work. (Less)

Performance of a short “magnetic bottle” electron spectrometer

In this article, a newly constructed electron spectrometer of the magnetic bottle type is described. The instrument is part of an apparatus for measuring the electron spectra of free clusters using synchrotron radiation. Argon and helium outer valence photoelectron spectra have been recorded in order to investigate the characteristic features of the spectrometer. The energy resolution (E/ΔE) has been found to be ∼30. Using electrostatic retardation of the electrons, it can be increased to at least 110. The transmission as a function of kinetic energy is flat, and is not impaired much by retardation with up to 80% of the initial kinetic energy. We have measured a detection efficiency of most probably 0.6(-0.1) (+0.05), but at least of 0.4. Results from testing the alignment of the magnet, and from trajectory simulations, are also discussed.

Simulations of light induced processes in water based on ab initio path integrals molecular dynamics. II. Photoionization

We have applied ab initio based reflection principle to simulate photoelectron spectra of small water clusters, ranging from monomer to octamer. The role of quantum and thermal effects on the structure of the water photoelectron spectra is discussed within the ab initio path integral molecular dynamics (PIMD) framework. We have used the PIMD method with up to 40 beads to sample the ground state quantum distribution at temperature T = 180 K. We have thoroughly tested the performance of various density functionals (B3LYP, BHandHLYP, M06HF, BNL, LC-ωPBE, and CAM-B3LYP) for the ionization process description. The benchmarking based on a comparison of simulated photoelectron spectra to experimental data and high level equation-of-motion ionization potential coupled clusters with singles and doubles calculations has singled out the BHandHLYP and LC-ωPBE functionals as the most reliable ones for simulations of light induced processes in water. The good performance of the density functional theory functionals to model the water photoelectron spectra also reflects their ability to reliably describe open shell excited states. The width of the photoelectron spectrum converges quickly with the cluster size as it is controlled by specific interactions of local character. The peak position is, on the other hand, defined by long-range non-specific solvent effects; it therefore only slowly converges to the corresponding bulk value. We are able to reproduce the experimental valence photoelectron spectrum of liquid water within the combined model of the water octamer embedded in a polarizable dielectric continuum. We demonstrate that including the long-range polarization and the state-specific treatment of the solvent response are needed for a reliable liquid water ionization description.

Ultrafast Hybridization Screening in Fe3+ Aqueous Solution

We report here on the electron binding energies and ultrafast electronic relaxation of the Fe(3+)(aq) complex in FeCl(3) aqueous solution as measured by soft X-ray photoelectron (PE) spectroscopy from a vacuum liquid microjet. Covalent mixing between the 3d valence orbitals of the iron cation and the molecular orbitals of water in the ground-state solution is directly revealed by spectroscopy of the highest partially occupied molecular orbitals. Valence PE spectra, obtained for photon energies near the iron 2p absorption edge, exhibit large resonant enhancements. These resonant PE features identify 3d-O2p transient hybridization between iron and water-derived orbitals and are an indication of charge transfer within the electronically excited Fe(3+)(aq)* complex. Charge transfer from water to iron is also revealed by the 2p core-level PE spectrum, and the asymmetric peak shape additionally identifies the characteristic multiplet interactions in the 2p core-hole state. The electronic structure of water molecules in the first hydration shell is selectively probed by Auger decay from water molecules, at excitation energies well below the O1s absorption edge of neat water. These experiments lay the groundwork for establishing resonant PE spectroscopy for the study of electronic-structure dynamics in the large family of transition metal (aqueous) solutions.