KLL auger and core level (1s and 2p) photoelectron shifts in a series of gaseous sulfur compounds

Core (1s and 2p) X-ray photoelectron shifts and KLL (¹D₂) Auger shifts for 22 sulfur compounds have been measured. The values have been correlated by means of atomic charge plus remote potential or central atom potential models. Either approach is equally effective tor binding energy correlations. The relaxation corrected and transition state models are in general superior to ground state models. Auger shift predictions are however poor in all cases. Absolute total static relaxation and extra-atomic relaxation values have been assessed by using the Auger parameter of Lang and Williams and relativistic atomic calculations for the free atom and its ions. These extra-atomic relaxation components are not additive but rather obey an average contribution behavior. The relaxation shift values have been compared with those obtained from the original Auger parameter (α) of Wagner. The correlation of 1s and 2p binding energies suggested a revised relationship for the Wagner Auger parameter and an equivalent simple form of the Lang and Williams parameter which can be used with satisfactory results when only the usual experimental binding energy (2p) is available in conjunction with the Auger shift.     

High energy xps using a monochromated Ag Lα source: resolution,sensitivity and photoelectric cross sections

Resolution, sensitivity and calibration data are presented for a novel high energy XPS source, monochromated Ag Lα radiation (hv = 2984.3 eV). Adequate resolution is attainable for good signal/noise spectra, whilst values for experimental sensitivity factors agree well with theoretical cross section values calculated by Nefedov. This allows an evaluation of ESCA 3 Mk. II transmission function up to 3000 eV, which appears to obey an approximate E^{$\text{?1}\text{2}$} dependence. Monochromated Ag Lα (linewidth 1.3 eV) overcomes the problem of broad natural linewidths for high energy sources, such that chemical state information can be gained. Various new core level and Auger peaks are developed, a notable feature being the 1s core level and KLL Auger transition capability from Al through to Cl. Improved sensitivity is experienced for elements whose major peaks occur in the 1500–3000 eV BE range, whilst there is no serious reduction of sensitivity in the conventional XPS energy range.     

Energies and chemical shifts of the sulphur 1s level and the KL2L3(1D2) Auger line in H2S,SO2 and SF6

The sulphur 1s binding energies and KL₂L₃(¹D₂) Auger energies have been measured in gaseous H₂S, SO₂ and SF₆. The experimental data, including the chemical shifts, are compared with various theoretical ab initio results. Theoretical and experimental values agree within 1-2 eV for the chemical shift and the binding energy of the 1s level, provided in the latter case relaxation, relativistic and correlation corrections are applied. Likewise, Shirley's method²⁰, which uses empirical energies, predicts the Auger energies satisfactorily. The measured S 1s binding energies are 2478.5(1) eV, 2483.7(1) eV and 2490.1(1) eV, and KL₂L₃(¹D₂) Auger energies are 2098.7(1) eV, 2095.5(2) eV, 2092.6(1) eV for H₂S, SO₂ and SF₆, respectively. The chemical shift for the 1s electron is found to be greater than for the 2s or 2p electron and in better accord with the prediction of the potential model. Data suggest the molecular relaxation energy to be small compared with the atomic relaxation energy.     

Estimating the adsorption energy of element 113 on a gold surface

We report first-principle based studies of element 113 (E113) interactions with gold aimed primarily at estimating the adsorption energy in thermochromatographic experiments. The electronic structure of E113-Au _n systems was treated within the accurate shape-consistent small core relativistic pseudopotential framework at the level of non-collinear relativistic density functional theory (RDFT) with specially optimised Gaussian basis sets. We used gold clusters with up to 58 atoms to simulate the adsorption site on the stable Au(111) surface. Stabilization of the E113-Au _n binding energy and the net Bader charge of E113 and the neighboring Au atoms with respect to n indicated the cluster size used was appropriate. The resulting adsorption energy estimates lie within the 1.0–1.2 eV range, substantially lower than previously reported values.     

Auger rates of second-row atoms calculated by many-body perturbation theory

Many-body perturbation theory is applied to calculate the KLL Auger rates of all terms of atoms C, N, F and Ne. Theoretical rates are compared with experiment and other theories for Ne and O. A new set of the Auger satellites, corresponding to the main photoelectron line binding energy is proposed. The intensities of these satellites are calculated and some of these satellites are identified in experimental KLL Auger spectra of Ne.     

Relaxation energies for photoionization of tellurium

The energies of the 3p, 3d, 4s, 4d, 5s and 5p photopeaks and of the M_{4, 5}NN and M_{4, 5}NO Auger peaks have been measured for tellurium metal. The associated relaxation energies were computed by two different methods, first, by comparing the measured binding energies with those calculated theoretically employing Koopman's theorem, and second, by a method devised by Shirley and co-workers. The merits of these two methods are examined by comparing measured MNN, MNO and KLL Auger energies with those calculated using the predicted relaxation energies.     

K Auger transitions of the free sodium atom

TheK Auger spectrum of the free sodium atom, following electron impact ionization, was measured with 0.16% resolution using a sodium atomic beam as target. The absolute energies and relative intensities ofKLL, KLM and numerous satellite transitions have been determined. The absolute energies of theKLL transitions of the free sodium atom were found to be smaller by 13.1 eV than the corresponding energies found for sodium in Na₂O (relative to the Fermi level) by Fahlmanet al. Also the relativeKLL intensities differed in two cases indicating solid state and/or chemical effects. The present relative intensities agree better with theoretical values calculated by McGuire, Walters and Bhalla, and Chen and Crasemann than those of Na₂O. In an Appendix the natural line widths of theKLL andKM-LLM transitions of sodium have been calculated.     

An XPS—AES study of gaseous xanthates and related sulfur-containing compounds

Core XPS spectra for carbon, oxygen, and sulfur and KLL Auger spectra for sulfur in CH₃OCS₂CH₃, (CH₃OCS₂)₂, CS₂, and OCS have been measured and relaxation shifts determined for the sulfur atoms by combining the S 1s measurement with the S KLL (¹D₂) measurement.Relaxation shifts of the sulfur atoms were also estimated from CNDO results for the neutral and core-ionized molecules using the equivalent cores approximation. The results are in qualitative agreement with the measurements, but exaggerate the relaxation by about 100%.The results show that the bonding of the (CH₃O-) group in the two xanthate compounds is very similar. The ionization energies of the S and -S- atoms within the xanthate molecules differ from each other by 1.5 eV; this difference arises almost entirely from the initial-state charge distribution rather than from final-state relaxation. However, the ionization energies of similarly bonded sulfur atoms are nearly the same. The effect of the oxygen atom on the bonding of the carbon and -S- atoms in the (-CS₂-) group in the xanthate compounds is to increase the (C 1s-S 2p_{$\text{3}\text{2}$}) ionization energy difference from the value reported for aliphatic disulfides.     

A qualitative and quantitative study of the oxides of aluminum and silicon using AES and XPS

Experimental AES and XPS results from powdered α-Al₂O₃, SiO₂, Al₂Si₂O₇·2H₂O and an aluminosilicate glass are presented. The AES kinetic energy and the XPS binding energy values of core-level states and the peak shapes of X-ray induced O KLL Auger transitions are presented as qualitative reference data for the purpose of aiding in the identification of unknown aluminum oxide/silicon oxide samples. The AES peak-to-peak heights and the XPS peak areas of core-level states are presented as quantitative data and are used in the calculation of empirical relative sensitivity factor values. In addition, the sensitivity factor values are given parameters according to a single variable, f₈, defined as the ratio of the volume density of the oxygen atoms to the sum of the volume densities of the aluminum and silicon atoms.     

Bremsstrahlung-induced Auger transitions and photoemission in elemental red phosphorus

Measurements of the Bremsstrahlung-inducedK-LL andK-LM Auger transitions in red phosphorus are reported and compared with semi-empirical data. The relative intensities of theK-LL lines are in excellent agreement with predictions based on the intermediate coupling scheme including configuration interaction. There is, however, a disagreement between the predicted and the experimental values of the kinetic energies. The origin of this discrepancy is due to inaccurate binding energy values used in earlier semiempirical estimations. Revised semi-empirical energy values based on reliable binding energies determined by internal and conventional x-ray photoemission are in excellent agreement with the experimental data. The energy of the x-rayK radiation is 2,013.8±0.4 eV, the Wagner's Auger parameter amounts to 1,987.2±0.1 eV in elemental red phosphorus, and to 1,983.9±0.5 eV in phosphorous oxide.     

Die Feinstruktur desL-MM-Auger-Elektronenspektrums von Argon und derK-LL-Spektren von Stickstoff,Sauerstoff und Methan

The fine structure ofL-MM Auger electron spectrum of argon andK-LL spectra of the gases N₂, O₂ and CH₄ was investigated with an electrostatical spectrometer. The ionisation was caused by the continuous X-radiation from a tungsten target. From the results of Auger electron energies measured, the binding energies of the electrons of the inner shells were calculated. The results obtained with argon agreed exactly with the known values. Further it could be shown, that the value of 400 eV for the binding energy of a 1s-electron in the N₂-molecule, so far obtained, must be replaced by the value (409,4±1,0) eV. A comparison between the relative intensities of fine structure lines and the theory of the Auger process given byAsaad andBurhop could not be carried out, because the Auger electrons, having in our experiment an angular distribution relativ to the incident X-ray beam, could only be measured between an angular range of 49,3° and 61,0°.     

The KLL and KLX auger electrons of arsenic from the 75Se decay

The KLL and KLX spectra for Auger electrons of arsenic (Z = 33) emitted during ⁷⁵Se decay were recorded, with an instrumental resolution of 11 eV, using a combined electrostatic spectrometer. The relative energies and intensities of nine KLL and ten KLX transitions were determined by computer analysis of the spectra. The margins of error were estimated to be 1–4 eV for energies and 2–50% for intensities. Except for the KL₁L₂ (¹P₁) transition, the measured relative intensities of the KLL transitions were found to agree, within 3 standard deviations (σ), with those calculated relativistically using the intermediate coupling approximation with configuration interaction. The discrepancy for the KL₁L₂ (¹P₁) transition amounted to 6σ. The KL₃M_2,3/KL₂M_2,3 transition intensity ratio agreed with the prediction based upon the intermediate coupling scheme but deviated by 7 σ from the value predicted by the jj coupling approximation.     

Study of the energy level structure for the isoelectronic series of scandium-like ions

The structure of the energy level system for 39 ions of the scandium isoelectronic sequence is studied on the basis of the relativistic self-consistent field method taking into account the configuration interaction. The Dirac-Fock equations are solved with subsequent diagonalization of the energy matrix. The ground-state ionization potentials are determined for each ion. The energy levels corresponding to the 3d4s ², 3d ²4s, and 3d ₃ configurations are also calculated. The obtained energy values are compared with the experimental data as well as with the results of calculations carried out by other authors.     

Details of the extended low energy structure in the oxygen K emission spectrum from MgO and CaO

A complicated low energy structure in the O K X-ray emission of MgO and CaO is reported. The onset of this structure falls at about 15 eV and some structure is discernible still at about 80 eV below the Kα line. The main features of this structure are interpreted as KLL radiative Auger transitions. Transitions from initial MO states, consisting mainly of metal p and ligand s wave functions, to the final O 1s state are proposed in CaO.     

KLL Auger and x-ray photoelectron spectra of phosphine,some phosphorus halides and the other hydrides isoelectronic with argon

KL₂L₃(¹D₂) Auger and 1s photoelectron energies have been measured for molecular hydrides isoelectronic with Argon (HCl, H₂S, PH₃ and SiH₄). In addition a detailed comparison of Auger and photoelectron shifts in a series of phosphorus halides (vs phosphine) has been undertaken using additional P_2p binding energies. The potential model is better able to predict 1s binding energy shifts with either ground state or relaxation corrected models than the 2p shifts. These latter values seem also to be reduced by shielding effects. In general, fluorides are better predicted than chlorides. Auger shifts correlate linearly(but not in a 1:1 relationship) with 1s photoelectron shifts throughout the isoelectronic series and also in the case of the phosphorus fluorides and phosphine. The two potential models, however, provide poor prediction of Auger shifts.     

Improved potential energy curve and vibrational energies for the electronic ground state of the hydrogen molecule

The potential energy curve for the electronic ground state of the hydrogen molecule has been recomputed for intermediate and large internuclear separations. for 2.4 ≤ R ≤ 8.0a.u. the previous potential energy curve has been improved. The largest improvement amounts to 5.5 cm^?1, and was obtained in the vicinity of R = 4.4a.u.. Using the new potential energy curve, and the adiabatic and relativistic corrections, the vibrational and rotational energy levels have been calculated for H₂, HD, and D₂. The deviations of the calculated energy levels G(v) of H₂ and D₂ from the observed values follow very closely the nonadiabatic corrections resulting from the Van Vleck formula.     

Study of chemical states at intergranular fracture planes of iron-phosphorus alloys by auger and electron energy-loss spectroscopies

Auger and electron energy-loss spectroscopies (ELS) have been used to study chemical states at the fracture surfaces of iron-phosphorus alloys. The transgranular (TG) and intergranular (IG) fracture planes have similar Auger P LVV transition energies and similar Fe 3p loss energies. These indicate that phosphorus and iron atoms are dispersed atomically in layers segregated at IG planes. The energy separations between the inter-and intra-atomic Auger transition peaks in P LVV show that the TG and IG planes and Fe₃P have similar energy separations between the P 3p and Fe 3p levels. The layers segregated at IG planes are estimated to be equivalent to a monolayer, as indicated by the dependence of the loss energy of the valence-conduction-band transition on primary-electron kinetic energy from 200 to 500 eV. The phosphorus concentration in the segregated layers is saturated to ~ 20 at.% above a bulk phosphorus concentration of 2 at.%.     

Characteristic electron energy loss structure for clean and oxidized chromium surfaces

AES and EELS spectra have been measured on clean and oxidized chromium surfaces. Auger peaks at 31.0 and 44.0 eV of the oxide are attributed to cross transitions between chromium and oxygen: {M_2,3(Cr)V(Cr)V(O)} and {M₁(Cr)L₁(O)V(Cr)} respectively. Core loss features are consistent with valence band structure with a newly observed loss peak at 41.1 eV for the oxidized surface being ascribed to a core exciton with binding energy E_b = 1.6 eV.     

Line shape analysis and relaxation energies in the MVV Auger spectra of zinc and zinc oxide

The oxidation of polycrystalline zinc has been studied by recording the evolution of the line shape of the corresponding Auger spectra. The fine structure of the surface-sensitive low energy M₁ VV and M₂₃VV (V = 4s ? 3d valence band) lines in pure zinc has been analyzed and a new feature involving the 4s band tentatively identified. In the course of oxidation the main peaks broaden and shift to lower energies. This behaviour is explained in terms of increase of the 3d band width and decrease in the extraatomic relaxation energies. The extraatomic relaxation is found to decrease in the oxide by ~3.8 eV. A derivation of Auger intra and Extraatomic energies involving basically experimental data is presented. These values are compared to theoretical evaluations and their connection with photoemission dynamical relaxation data is discussed.     

Plasmon energy gain and double ionization satellites in the Be Auger spectrum

Two relatively weak, higher energy satellites are observed at 18 and 38 eV above the Be KVV Auger spectrum. The lower energy satellite is assigned to coupling of energy from bulk plasmon de-excitations $\text{(}\text{h}\text{?}\text{ω ～ 18 eV)}$ with Auger electrons and the higher energy event to Auger electrons ejected from Be atoms with doubly ionized K levels.