Calculation of sulphur L(S2p)-MM Auger energies of H2S

The Auger energies of the L(S2p)-MM transitions of H₂S have been computed using MC SCF methods. The results are sufficiently accurate to assign the experimental spectrum and indicate large relaxation as well as large single-triplet splitting for low energy transitions.     

Effect of phosphorus concentration on the electronic structure of nanocrystalline electrodeposited Ni–P alloys: an XPS and XAES investigation

A surface analysis has been conducted on a series of electrodeposited nickel‐phosphorus (Ni–P) alloys containing from 6 to 29 at.% phosphorus, using X‐ray photoelectron spectroscopy (XPS) and X‐ray excited Auger electron spectroscopy (XAES). No changes in core‐level binding energies, Ni2p3/2 and Ni2p1/2, P2p, P2s, or X‐ray excited NiLMM and PKLL Auger lines were observed regardless of phosphorus concentration. The only systematic differences observed concerned: (i) the binding energy of the Ni2p satellite peak, (ii) the fine structure of the NiLMM Auger lines, (iii) the percentage of the satellite in the total Ni2p3/2 spectrum and (iv) the valence band density of states in the Ni3d electrons region, all related to the electronic structure of the Ni–P alloys. For the first time, it has been possible to describe and rationalise the influence of (phosphorus) ligand concentration on the electronic structure of nickel‐based alloys, using a screening model proposed in the literature for clarifying the role of substituents on the electronic structure of conductor compounds of nickel. As the phosphorus content increases, the number of non‐bonding Ni3d electrons decreases. Thus the d‐type core‐hole screening is less pronounced and the binding energy of the satellite for the final state with a filled Ni4s shell increases. Copyright © 2008 John Wiley & Sons, Ltd.     

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.     

Study of nonradiative decay properties following resonant double excitation to the [1s2p]nln′l′ states of Ne atom using soft X-ray undulator radiation

We investigate the nonradiative decay properties of resonantly photoexcited [1s2p]nln′l′ (n,n′≧3) states of Ne atom, where square brackets indicate hole states, using soft X-ray undulator radiation. Partial ion-yield spectra for the Ne²⁺–Ne⁴⁺ ions were measured in the region of double excitation resonance by means of time-of-flight spectrometry. The Ne³⁺ partial ion-yield spectrum has been found to reveal resonant enhancements at the energy positions of doubly excited states, which implies the most plausible decay channels leading to the third step Auger processes. Energy diagram of the excited and relaxed states associated with the [1s2p](³P)3p² doubly excited state of the neutral Ne as well as the Ne ions was calculated based on the multiconfiguration Dirac–Fock (MCDF) method in order to interpret the possible nonradiative decay channels. The low-energy electron spectrum originated from the second/third step Auger processes was preliminarily measured to show a rich structure induced at the [1s2p](³P)3p² double excitation resonance.     

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.     

Many-electron contributions in the auger spectrum of CO

The CO Auger electron spectrum has been re-investigated by means of ab initio MO LCAO calculations using a combined SCF CI procedure. The CI comprises internal and semi-internal contributions to the final double-hole Slate wave-functions. In particular, the latter contributions are found to be highly significant both with respect to energies and intensities of the Auger transitions. In order to compare with the experimental spectra, the intensities of the transitions have also been calculated using a simple one-center model.     

SCF and limited CI calculations for assignment of the Auger spectrum and of the satellites in the soft X-ray spectrum of H2O

SCF and limited CI calculations have been performed for a number of excited states of doubly ionized water. The calculations allowed an assignment of both the Auger spectrum and most of the satellites in the soft X-ray spectrum. The assignment for the two highest peaks in the Auger spectrum was ambiguous. SCF calculations of the K emission spectrum of H₂O were also performed. It was found that limited CI calculations were of importance for some states with two open shells in one symmetry. Such effects are caused by large off-diagonal lagrangian multiplies connecting the open shells in the reference configuration.     

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.     

The electronic spectrum of the UO2 molecule

The electronic spectrum of the UO(2) molecule has been determined using multiconfigurational wave functions together with the inclusion spin-orbit coupling. The molecule has been found to have a (5fphi)(7s), (3)Phi(2u), ground state. The lowest state of gerade symmetry,( 3)H(4g), corresponding to the electronic configuration (5f)(2) was found 3330 cm(-1) above the ground state. The computed energy levels and oscillator strengths were used for the assignment of the experimental spectrum in the energy range 17,000-19,000 and 27,000-32,000 cm(-1).     

On the doubly ionized states of Ar2 and their intra- and interatomic decay to Ar2 3+

Potential energy curves of the Auger state Ar+(2p(-1))-Ar, the different one- and two-site dicationic states Ar2 ++ (with energies in the range of 32-77 eV), and the lowest two-site tricationic states Ar++ - Ar+ (with energies in the range of 64-76 eV) computed using elaborated ab initio methods are reported. The accessible relaxation channels of the electronic states of Ar++ - Ar populated by Auger decay are studied. In particular, we study in detail the interatomic Coulombic decay following the population of one-site satellite states of Ar++(3s(-1)3p(-1))-Ar recently observed experimentally. Other relaxation pathways of Ar++ - Ar, including radiative charge transfer, nuclear dynamics through curve crossing, and intra-atomic decay processes are also investigated.     

用交叉分子束研究O(^3p)与CF2=CFCl,CF2=CFBr,CF2=CH2的反应

本文报道在交叉分子束装置中, 研究氧原子和CF2=CFCl, CF2=CFBr,CF2=CH2的反应。在O(^3p)和CF2=CFBr(或CF2=CFBr)反应中, 首次观察到反应生成的CF2(^3B1)的发射光谱, 而在O与CF2=CH2反应中, 用激光诱导荧光方法检测到CFH卡宾, 确定了在此反应中CFH卡宾的生成, 这一结果未见文献报道。并根据这些结果, 分析和讨论了在这些反应中, 生成CF2(^3B1)和CHF卡宾的机理。     

Energy levels, Auger branching ratios, and radiative rates of the core-excited states of B-like carbon

Energy levels, Auger branching ratios, and radiative rates of the core-excited states of B-like carbon are calculated by the saddle-point variation and saddle-point complex-rotation methods. Relativistic and mass polarization corrections are included using first-order perturbation theory. Calculated Auger channel energies and branching ratios are used to identify high-resolution Auger spectrum in the 300-keV C(+) → CH(4) collision experiment. It is found that Auger decay of these five-electron core-excited states gives significant contributions to Auger spectrum in the range of 238-280 eV.     

H2S ultrafast dissociation probed by energy-selected resonant Auger electron-ion coincidence measurements

We have studied the ultrafast dissociation of the H2S molecule upon S 2p3/2-->6a1 inner-shell excitation by combining high-resolution resonant Auger spectroscopy and energy-selected Auger electron-ion coincidence measurements. Auger final states have been correlated to the different fragmentation pathways (S+, HS+, and H2S+ ions). As an original result, we evidence a three-step mechanism to describe the resonant production of S+: the Auger recombination in the HS* fragment is followed for the A 3Pi and c 1Pi states by the S++H fragmentation mechanism.     

Positive-ionization decay of the carbon k-shell excited negative-ion resonance in co

The resonant state CO-(Cls)^-1 (2pπ)². first reported by King has been observed to decay by multiple Auger effect in all the positive-ionization channels of CO. The relative abundances for the resonant formation of CO⁺. CO²⁺. C⁺. O⁺, C²⁺ ions have been measured. the decay to neutral states by normal Auger transitions is observed in the (O- + C⁺ ion-pair formation.     

Monte Carlo simulation of full energy spectrum of electrons emitted from silicon in Auger electron spectroscopy

A Monte Carlo simulation including surface excitation, Auger electron‐ and secondary electron production has been performed to calculate the energy spectrum of electrons emitted from silicon in Auger electron spectroscopy (AES), covering the full energy range from the elastic peak down to the true‐secondary‐electron peak. The work aims to provide a more comprehensive understanding of the experimental AES spectrum by integrating the up‐to‐date knowledge of electron scattering and electronic excitation near the solid surface region. The Monte Carlo simulation model of beam–sample interaction includes the atomic ionization and relaxation for Auger electron production with Casnati's ionization cross section, surface plasmon excitation and bulk plasmon excitation as well as other bulk electronic excitation for inelastic scattering of electrons (including primary electrons, Auger electrons and secondary electrons) through a dielectric functional approach, cascade secondary electron production in electron inelastic scattering events, and electron elastic scattering with use of Mott's cross section. The simulated energy spectrum for Si sample describes very well the experimental AES EN(E) spectrum measured with a cylindrical mirror analyzer for primary energies ranging from 500 eV to 3000 eV. Surface excitation is found to affect strongly the loss peak shape and the intensities of the elastic peak and Auger peak, and weakly the low energy backscattering background, but it has less effect to high energy backscattering background and the Auger electron peak shape. Copyright © 2014 John Wiley & Sons, Ltd.     

X-ray and electron induced Auger processes for I2 adsorption on uranium

The accurate determination of the kinetic energy of X-ray induced Auger electrons, which is necessary in XPS experiments, e.g. for calculating the Auger parameter, is sometimes hampered by peak interferences or by the high secondary electron background. The latter is of special importance for low kinetic energy electrons like e.g. the U(OPV) and U(OVV) Auger electrons. These problems can be circumvented by using electron induced Auger transitions (AES). However, since XPS and AES use different reference points for the energy scales, both scales have to be matched. This can be done by measuring the kinetic energy of an appropriate Auger transition in XPS and relating this value to the maximum of the second derivative of the same peak in AES.     

The Auger electron spectrum of water vapour

The Auger electron spectrum of water vapour has been recorded and analyzed. For the analysis, an approximate formula for calculating the intensities of the Auger electron lines is derived. It is shown, that the calculated intensities along with theoretical energies of the Auger transitions account well for the observed spectrum. In particular, new assignments in terms of transitions to triplet final states are suggested.     

Influence of formation path on the CH2BrCl2+ dissociation dynamics

To get further insight into the CH2BrCl site-selective fragmentation previously observed upon inner-shell ionization, we have performed high-resolution Br 3d and Cl 2p Auger and spin-orbit resolved Br 3d Auger spectra, and studied the dissociation properties of the CH2BrCl2+ dication formed at threshold by means of threshold electron pair-ion coincidence measurements. The key point is that the origin of site-specific bond breaking is found in the Auger decay itself, as it preferentially populates selected dication states. Whereas the predominance of the C-Br bond breaking is observed in both threshold and inner-shell studies, no signature of selective C-Cl rupture is reported for the dication formed at threshold.     

Configuration interaction in the L2,3—MM Auger spectrum of HCl and Ar

The L_2,3—MM Auger spectra of HCl and Ar have been calculated. Strong interaction between the Auger diagram state 4σ^?2 and correlation states explains the absence of the L_2,3—M₁² peak in the HCl spectrum. For argon semi-internal CI reproduces the high-kinetic-energy region, while a fairly large expansion of configurations is necessary to reproduce the low-kinetic-energy part of the spectrum.