Site-selected Auger electron spectroscopy of N2O

The N 1s Auger spectra for the two nonequivalent N atoms in N2O have been measured via Auger electron-photoelectron coincidence spectroscopy. The site-selected Auger spectra are compared with the normal Auger spectrum and with accurate theoretical calculations accounting for the effects of the dynamics of the nuclei on the energy and linewidth of the Auger bands. Such effects are found to be crucial factors in determining the different band shapes in the site-selected spectra.     

Calculations on the auger spectra of ethylene and acetylene

The Auger spectra of ethylene and acetylene have been calculated by a method including electron correlation at the ab initio level. Explicit assignments are given for both spectra. The results show that correlation effects leading to a breakdown of the two-hole picture for the final states of the Auger process are important in most parts of the spectra.     

Radiative auger effect and extended X-ray emission fine structure (EXEFS).

Radiative Auger spectra are weak X-ray emission spectra near the characteristic X-ray lines. Radiative Auger process is an intrinsic energy-loss process in an atom when a characteristic X-ray photon is emitted, due to an atomic many-body effect. The energy loss spectra correspond to the unoccupied conduction band structure of materials. Therefore the radiative Auger effect is an alternative tool to the X-ray absorption spectroscopy such as EXAFS (Extended X-ray Absorption Fine Structure) and XANES (X-ray Absorption Near Edge Structure), and thus it is named EXEFS (Extended X-ray Emission Fine Structure). By the use of a commercially available X-ray fluorescence spectrometer or an electron probe microanalyzer (EPMA), which are frequently used in materials industries, we can obtain an EXEFS spectrum within 20 min. The radiative Auger effect, as an example, demonstrates that the study on atomic many-body effects has become a powerful tool for crystal and electronic structure characterizations. The EXEFS method has already been used in many industries in Japan. Reviews about the applications and basic study results on the radiative Auger effect are reported in this paper.     

Summary of ISO/TC201 standard: ISO/TR 18394:2006—surface chemical analysis—Auger electron spectroscopy—derivation of chemical information

ISO/TR 18394 provides guidance for the identification of chemical effects on x‐ray or electron‐excited Auger electron spectra as well as for applications of these effects in chemical characterization of surface/interface layers of solids. In addition to elemental composition, information can be obtained on the chemical state and the surrounding local electronic structure of the atom with the initial core hole from the changes of Auger electron spectra upon the alteration of its local environment. The methods of identification and use of chemical effects on Auger electron spectra, as described in this Technical Report, are very important for accurate quantitative applications of Auger electron spectroscopy. Copyright © 2007 John Wiley & Sons, Ltd.     

Auger decay calculations with core-hole excited-state molecular-dynamics simulations of water

We report a new theoretical procedure for calculating Auger decay transition rates including effects of core-hole excited-state dynamics. Our procedure was applied to the normal and first resonant Auger processes of gas-phase water and compared to high-resolution experiments. In the normal Auger decay, calculated Auger spectra were found to be insensitive to the dynamics, while the repulsive character of the first resonant core-excited state makes the first resonantly excited Auger decay spectra depend strongly on the dynamics. The ultrafast dissociation of water upon O(1s)-->4a(1) excitation was analyzed and found to be very sensitive to initial vibrational distortions in the ground state which furthermore affect the excitation energy. Our calculated spectra reproduce the experimental Auger spectra except for the Franck-Condon vibrational structure which is not included in the procedure. We found that the Auger decay of OH and O fragments contributes to the total intensity, and that the contribution from these fragments increases with increasing excitation energy.     

Localized versus delocalized excitations just above the 3d threshold in krypton clusters studied by Auger electron spectroscopy

We present Auger spectroscopy studies of large krypton clusters excited by soft x-ray photons with energies on and just above the 3d(52) ionization threshold. The deexcitation spectra contain new features as compared to the spectra measured both below and far above threshold. Possible origins of these extra features, which stay at constant kinetic energies, are discussed: (1) normal Auger process with a postcollision interaction induced energy shift, (2) recapture of photoelectrons into high Rydberg orbitals after Auger decay, and (3) excitation into the conduction band (or "internal" ionization) followed by Auger decay. The first two schemes are ruled out, hence internal ionization remains the most probable explanation.     

Many-body theory of the Auger Auger-electron coincidence spectroscopy (AAECS) spectra of solids

A pair of Auger electrons generated, respectively, by creation and annihilation of the same multiple-hole state can be collected in coincidence by Auger Auger-electron coincidence spectroscopy (AAECS). In the present paper a many-body theory of AAECS spectra generated by Auger cascade decays in which the lifetime of a core-hole acts as an internal clock for the screening mechanism is formulated by treating photoelectrons and Auger electrons on the same footing. The unexploited basic spectral features of AAECS spectra of solids are elucidated by the present theory to show how the core-hole screening (delocalization of a valence hole) will affect the coincidence spectral lineshape.     

Metastable states in NO2+ probed with Auger spectroscopy

High-resolution N 1s and O 1s photoelectron spectra (PES) of NO are presented together with spectra of the subsequent Auger decay. The PES are analyzed by taking spin-orbit splitting of the (2)Π ground state into account providing detailed information on equilibrium distances, vibrational energies, and lifetime widths of the core-ionized states. In the Auger electron spectra (AES) transitions to five metastable dicationic final states are observed, with two of them previously unobserved. A Franck-Condon analysis of the vibrational progressions belonging to these transitions provides detailed information on the potential-energy curves of the dicationic final states as well as on the relative Auger rates. The present calculations of the potential-energy curves of NO(2+) agree well with the experimental results and allow an assignment of the two hitherto unresolved Auger transitions to excited states of NO(2+), C(2)Σ(+)and c(4)Π.     

Chemical shifts of auger electron lines and electron binding energies in free molecules. Sulfur compounds

The first paper describing a series of systematic investigations of the chemical shifts in Auger electron spectra from various free molecules is presented. Excitation is performed by means of a fine focus electron beam. The Auger electrons are retarded in a four component lens system and recorded at high resolution in a new multidetector system placed in the focal plane of the ESCA instrument. A calibration procedure against the KL₂L₃ Auger electron line of Ne is described. The first study concerns Auger electron line shifts for sulfur in some small molecules and the results are compared to the corresponding chemical shifts in the core photoelectron spectra. A formalism based on a transition potential model is briefly presented which takes account of the relaxation energies involved in Auger transitions as well as in single photoionization.     

Auger decay of molecular double core-hole state

We report on theoretical Auger electron kinetic energy distribution originated from sequential two-step Auger decays of molecular double core-hole (DCH) state, using CH(4), NH(3), and H(2)CO molecules as representative examples. For CH(4) and NH(3) molecules, the DCH state has an empty 1s inner-shell orbital and its Auger spectrum has two well-separated components. One is originated from the 1st Auger transition from the DCH state to the triply ionized states with one core hole and two valence holes (CVV states) and the other is originated from the 2nd Auger transition from the CVV states to quadruply valence ionized (VVVV) states. Our result on the NH(3) Auger spectrum is consistent with the experimental spectrum of the DCH Auger decay observed recently [J. H. D. Eland, M. Tashiro, P. Linusson, M. Ehara, K. Ueda, and R. Feifel, Phys. Rev. Lett. 105, 213005 (2010)]. In contrast to CH(4) and NH(3) molecules, H(2)CO has four different DCH states with C1s(-2), O1s(-2), and C1s(-1)O1s(-1) (singlet and triplet) configurations, and its Auger spectrum has more complicated structure compared to the Auger spectra of CH(4) and NH(3) molecules. In the H(2)CO Auger spectra, the C1s(-1)O1s(-1) DCH → CVV Auger spectrum and the CVV → VVVV Auger spectrum overlap each other, which suggests that isolation of these Auger components may be difficult in experiment. The C1s(-2) and O1s(-2) DCH → CVV Auger components are separated from the other components in the H(2)CO Auger spectra and can be observed in experiment. Two-dimensional Auger spectrum, representing a probability of finding two Auger electrons at specific pair of energies, may be obtained by four-electron coincidence detection technique in experiment. Our calculation shows that this two-dimensional spectrum is useful in understanding contributions of CVV and VVVV states to the Auger decay of molecular DCH states.     

X-ray absorption and resonant Auger spectroscopy of O2 in the vicinity of the O 1s-->sigma* resonance: experiment and theory

We report on an experimental and theoretical investigation of x-ray absorption and resonant Auger electron spectra of gas phase O(2) recorded in the vicinity of the O 1s-->sigma(*) excitation region. Our investigation shows that core excitation takes place in a region with multiple crossings of potential energy curves of the excited states. We find a complete breakdown of the diabatic picture for this part of the x-ray absorption spectrum, which allows us to assign an hitherto unexplained fine structure in this spectral region. The experimental Auger data reveal an extended vibrational progression, for the outermost singly ionized X (2)Pi(g) final state, which exhibits strong changes in spectral shape within a short range of photon energy detuning (0 eV>Omega>-0.7 eV). To explain the experimental resonant Auger electron spectra, we use a mixed adiabatic/diabatic picture selecting crossing points according to the strength of the electronic coupling. Reasonable agreement is found between experiment and theory even though the nonadiabatic couplings are neglected. The resonant Auger electron scattering, which is essentially due to decay from dissociative core-excited states, is accompanied by strong lifetime-vibrational and intermediate electronic state interferences as well as an interference with the direct photoionization channel. The overall agreement between the experimental Auger spectra and the calculated spectra supports the mixed diabatic/adiabatic picture.     

An interpretation of the O2 Auger electron spectrum

The Auger electron spectrum of O₂ is interpreted by comparing with other spectra, such as the photoelectron spectrum, the electron impact mass spectrum, and the double charge transfer spectrum. Each of these four spectra obeys its own selection rule; the difference in the selection rules plays a key role in our interpretation. Auger decays following a core shake-up excitation are identified in the O₂ spectrum for the first time. Many of the previous assignments are revised.     

Binding and L23MM auger energies in atomic and metallic zinc

An analysis of the photoelectron and photon-induced L₂₃MM Auger spectra of Zn metal has been performed. The relaxation processes involved in the Auger transitions have been investigated. They account well for the experimental Auger energies.     

Quantitative surface analysis by X-ray photoelectron spectroscopy and X-ray excited auger electron spectroscopy

It is shown that X-ray excited KLL Auger electron spectra allow it to describe measured signal strengths similarly to X-ray photoelectron signals, thus offering valuable information on the quantitative surface composition of a solid sample. The principal equation and corresponding fundamental parameters are discussed. As a result Auger spectra of C, N, O, F, and Na can be easily used in a multiline approach for quantitative analysis. LMM and MNN spectra give rise to more problems, due to their more complicated structure, uncertainties with regard to the background and the influence of Coster-Kronig transitions. These problems are overcome by the use of empirical ratios of the strongest lines of 2p/LMM or 3d/MNN. Since these ratios are independent of sample composition, they allow it to transform the Auger signal into the corresponding photoelectron signal, provided that a standard sample has been measured. Thus a true additional information is obtained and moreover difficulties in cases of photoelectron spectra with overlapping lines from other chemical elements can be overcome.Dedicated to Professor Günther Tölg on the occasion of his 60th birthday     

Auger photoelectron coincidence spectroscopy using synchrontron radiation

The technique of Auger-photoelectron coincidence spectroscopy (APECS) is described and illustrated with a case study of the Cu(100) 3p and M₂₃VV spectra. APECS offers many advantages over the conventional singles spectroscopy such as isolating overlapping spectral features, reducing secondary electron background, and revealing new decay modes. In the coincidence Cu Auger spectra discussed here, the multiplet structure of the quasi-atomic 3d⁸ Auger final state is clearly observed, as well as different intensities for the multiplet components for the p_1/2 and p_3/2 transitions. Furthermore, the spectra reveal evidence for a Coster-Kronig decay channel for 3p_1/2 core holes, and illustrate that the sum of the Auger electron and photoelectron kinetic energies is conserved. Possible technical improvements that can increase the counting efficiency are also discussed.     

Resonant Auger spectroscopy at the carbon and nitrogen K-edges of pyrimidine

The resonant Auger electron spectra obtained after photoexcitation below the C and N 1s ionization thresholds in the pyrimidine molecule have been measured at several photon energies. The results show the relevance of the localization of the inner hole and of the matching between the symmetries of the intermediate and final states in the decay spectra via participator transitions. The comparison with the Auger electron spectra suggests some assignment for the two-hole-one-particle states reached via spectator transitions. The analysis of the participator decay is supported by state-of-the art density functional theory calculations.     

Neue Methode zur quantitativen Analyse von AES-Spektren

Summary The quantitative analysis of Auger electron spectra may lead to problems using Auger peak-to-peak heights (APPH), especially in connection with chemical peak deformation and peak overlap. To eliminate these problems a method has been developed and was applied to metalnonmetal compounds. An integral spectrum is fitted with reference spectra and correction spectra, background differences are compensated. To deal with chemical effects a digital filter process is used. In order to test this method a copper-palladium alloy series has been measured and evaluated according to this method. The results show that a more accurate quantification could be obtained than by using APPHs and sensitivity factors. As a further advantage, relative sensitivity factors are no longer necessary due to peak/background standardization.     

Radiationless decay in the region of the 2t2g and 4eg resonances in SF6

The S 2p Auger spectrum of SF(6) has been studied in the region of the 2t(2g) and 4e(g) resonances. The partial Auger spectra due to the ionization of the 2p spin-orbit components and of a shake-up satellite state have been measured selectively by tuning the photon energy and using the Auger electron-photoelectron coincidence technique. A detailed analysis of the Auger spectrum has also been performed using the Green's function-based second-order algebraic diagrammatic construction method.     

Theory of lineshape in photoelectron and Auger spectra

A theory of lineshape in photoelectron spectra is developed based on the Green’s function calculation of the atomic vacancy structure. It is shown that the broadening of photoelectron lines is always somewhat asymmetrical, and the broadening of satellite lines arising in atomic photoionization is generally strongly asymmetrical and inverse. The approach is generalized to low-energy Auger spectra; it is shown that Auger decay lines of excited atomic states may narrow with respect to the width of the initial level. The results are compared with experimental photoelectron spectra. Translated fromZhurnal Strukturnoi Khimii, Vol. 39, No. 6, pp. 985–991, November–December, 1998.     

Study of M4,5N4,5N4,5 auger energy shifts of Cs and I in free CsI molecules

High-resolution electron beam excited M_4,5N_4,5N_4,5 Auger electron spectra of Cs and I have been measured from CsI vapour. The Auger energies of both Cs and I observed from gaseous CsI are higher than the corresponding free-atom energies due to extra-atomic relaxation. The molecular Auger results have been compared with corresponding photoelectron measurements and free-atom data. Estimates for extra-atomic relaxation energies have been extracted from the changes of the Auger parameter between molecular and atomic species and from the difference between experimental energies and energies calculated with a relativistic Dirac-Fock program, applying the point-charge model for the CsI molecule.