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.     

Determination of effective atomic charge,extra-atomic relaxation and madelung energy in chemical compounds on the basis of X-ray photoelectron and auger transition energies

A new method is proposed for the determination of effective atomic charge, extra-atomic relaxation, and Madelung energy in chemical compounds, based on the experimentally measured energies of X-ray photoelectron and Auger transitions. The method has been applied to solid compounds of the elements from Na to Cl, and to a number of free sulfur-, phosphorus-, silicon-, and chlorine-containing molecules. The experimental energies are represented as consisting of two parts. The first part is determined by the ionization energy of a free ion with a given effective charge, and includes the intra-atomic relaxation. The second part is determined by the Madelung energy and the extra-atomic relaxation. The first contribution is calculated by using the Hartree-Fock method. The effective atomic charges required have been found from the shifts of Kα-lines in the X-ray spectra. The extra-atomic relaxations are obtained as the differences between experimental and theoretical Auger parameters, and the values calculated are the additive functions of ligands of the atom studied. The increments of the additive scheme correlate with the ligand refractions. The effective charges, extra-atomic relaxation energies and Madelung potentials obtained from ESCA and AES data agree well with both calculated and direct experimental results.     

Characterization of silicon compounds using the Auger parameter in X-ray Photoelectron Spectroscopy (XPS)

The Auger parameter is demonstrated to be valid for determining the change in the extra-atomic relaxation energy and is applied to the characterization of silicon dielectric thin layers. The changes in extra-atomic relaxation energy on going from Si to SiN_1.3 and to SiO₂ derived from the Auger parameter are -1.1 and -2.0 eV, respectively. These values are in good agreement with those derived from the polarization energy by Mott et al. The relationship between the polarizability and the Auger parameter is linear. Using the Auger parameter in XPS is a powerful and excellent method to determine the dielectric constant of very thin (⪅100 Å) silicon insulators since the electron escape depth is very small (⪅20 Å).     

Electronic relaxation processes in the KLL′ auger spectra of the free magnesium atom,solid magnesium and MgO

The K-Auger spectrum of the free magnesium atom and the magnesium metal is calculated. The Friedel model is used to account for extra-atomic relaxation effects. Theoretical Auger electron energies are compared with the corresponding experimental values. In general the agreement between theory and experiment is good.The evolution of the extra-atomic relaxation energy in going from the metal to the oxide is presented.     

The use of monochromatic Ag Lα radiation to study relaxation energy differences in X-ray photoelectron spectroscopy of alkali metal chlorides

Monochromatic Ag Lα radiation has been used to measure the Cl 1s, Cl 2p and Cl KLL Auger energies by XPS in a series of alkali metal chlorides. The extra-atomic relaxation energies derived from these data were found to be linearly related to the polarizability of the metal—chloride bond. The magnitudes of the extra-atomic relaxation energies associated with photoemission from the Cl 1s and Cl 2p levels conformed with the Slater screening coefficients for these orbitals.     

Auger kinetic energies and electronic relaxation phenomena in atoms and solids

A semi-empirical theory has been developed to calculate the kinetic energy of Auger electrons resulting from radiationless transitions in both free atoms and metals. Experimental electron binding energies and calculated two-electron interaction and relaxation energies are used. Relaxation energies are determined by means of hyper-Hartree—Fock hole-state calculations. To account for extra-atomic relaxation phenomena in metals, it is assumed that conductionband electrons occupy free-atom-like screening orbitais. The relationship of the present theory to recent work of Shirley et al., Larkins, Kim et al. and Watson et al. is discussed. The dependence of the Auger cross-relaxation energy on the ionicity of compounds is briefly discussed.     

X-ray photoelectron spectroscopy of quick-frozen aqueous solutions of sodium salts

X-ray photoelectron spectra were observed on the quick-frozen aqueous solutions of sodium halides. The separation between Na KLL Auger peak and Na 1s peak was found to be different between the quick-frozen aqueous solution and the crystal of the salt, while the separation of Na 1 s peak and a core-electron peak of anion little differs between the two states.Discussion is given on the extra-atomic relaxation energy and other energy terms which are affecting the shifts of KLL Auger and core-electron peaks.     

A study of atomic iodine and molecular thallium iodide by X-ray photoelectron and auger electron spectroscopy

The I3d5/2 binding energy has been measured in atomic iodine, thallium iodide and cesium iodide by high temperature gas-phase photoelectron spectrscopy using Al K (1486.6 eV) X-rays. The iodine M₅N_4,5N_4,5 (¹G₄) Auger energies for TlI and CsI have also been measured and combined with binding energies to yield extra-atomic relaxation energies of 0.5 and O.3 eV, respectively, after corrections are applied to the Auger parameter. Charges were calculated using the simple potential model, which was also used to obtain an estimate of the atomic T14f binding energy. Two other estimates of the atomic T14f7/2 binding energy have also been calculated, both based on Dirac-Fock ΔSCF binding energies. The results of the three methods suggest a value of 125.3 ± 0.2 eV for T14f7/2.     

Relaxation energies of oxygen auger transitions in some oxides

Relaxation effects are of major importance in the so-called chemical shifts observed in XPS and AES. These chemical shifts mainly arise from changes in the electrostatic environment due to the field of the neighbouring atoms in the initial neutral state and from electron redistribution in the surrounding electron cloud in order to screen the final state holes of the excited atom. Using a three-step model for the Auger process, we succeeded in deriving cross-relaxation energies from the KLL spectrum of oxygen in oxides, provided a careful calibration of experimental binding and Auger kinetic energies is achieved. It has been shown that the extra-atomic relaxation energy increases with ionicity for oxides of non-transition metals. In the case of transition metal oxides, it has been found that the cross-relaxation energies are larger than for the other oxides; it is believed that this is due to a more efficient screening effect of the d-electrons of the neighbouring metal atoms.     

Cluster growth of Cu on graphite: XPS,Auger and electron energy loss studies

Auger, XPS and EELS techniques have been used to investigate the core levels, the d-valence band and the electronic transitions of different UHV deposited Cu clusters on graphite. The decreasing of the Cu particle size produces core levels and valence band shifts towards higher binding energies. Lower extra-atomic screening of the conduction electrons near the excited atom and shift of the d-band towards the isolated atom levels are claimed to explain these effects. The EELS results suggest that, for smallest clusters, no structural change but only a lattice parameter contraction of the f.c.c. cage occur.     

Vapour phase M4,5N4,5N4,5 Auger electron spectra of antimony and tellurium

High resolution M_4,5N_4,5N_4,5 Auger electron spectra from Sb₄ and Te₂ vapours have been measured using electron impact excitation. The spectra have been decomposed into line components and relative intensities and energies of the components are compared with calculated intensities and energies. The calculations have been done for these molecular samples using the free-atom calculation model involving initially filled shells. The calculations have been treated in the mixed coupling scheme using jj coupling for initial state and intermediate coupling for the final state. The experimental results agree well with the calculated values, indicating that the molecular effects on the relative intensities and energies are very small for these core level transitions. The clear molecular effects are found in the broadening of lines and in the kinetic energy shifts due to extra-atomic relaxation effects.     

Relationship between the auger parameter and the energy gap

In this communication we show that for different semiconductors which do not contain transition metal ions, the shift in the extra-atomic relaxation energy for the metal ion with the core hole-as measured by the Wagner Auger parameter shift with respect to the metallic state-is roughly linearly correlated to the energy gap with a slope approximately equal to −1. The relationship, useful from a practical point of view, can be rationalized using the qualitative concepts of local and non-local screening developed by Veal and Paulikas and the direct relation between the band gap and anion electronegativity.

The core-hole screening for the semiconductors that follow the correlation can be described by the non-local screening mechanism. In this case, the polarized ligands transfer electronic charge to the unfilled s-p metal orbitals which are pulled down to the energy level of the local anion valence band by the core hole. Semiconductors containing transition metal ions, for which local screening mechanisms can occur by transferring the charge from the ligands to the localized d electronic levels, do not follow the correlation. This is due to the fact that the Auger parameter of the cation in the compound is similar to that of the atom in the metallic state. This result indicates that the relaxation energy in the transition metal compounds can be similar to the screening energy in the metallic state.     

Extra-atomic electronic cross-relaxation energies in KL2,3L2,3 Auger transitions in small sodium clusters from SCF-Xα-SW calculations

The self-consistent-field-Xα-scattered-wave method is used to calculate extra-atomic electronic cross-relaxation energies R_C^ea involved in KL_2,3L_2,3 Auger transitions in a series of small sodium clusters. R_C^ea is shown to increase with increasing dimension of the cluster. The R_C^ea value for Na₁₅ already closely approaches the metallic value. It is felt that the present calculational method will also be useful in determining relaxation energies in chemisorption systems.     

The effect of relativistic curvature calibration corrections for a non-retarding hemispherical sector analyzer: revision of the absolute S1s binding energy of H2S and the KLL auger energy of PH3

Application of required curvature corrections to the linear (relativistic) calibration procedure previously employed reduce (by 0.48 eV) the reported Sis binding energy of H₂S to 2478.43 eV and the S KLL Auger energy (by 0.01 eV) to 2098.55 eV. Only the former value is significantly altered. For phosphorus compounds, the P1s binding energy of PH₃ is essentially unchanged at 2150.87 eV but the P KLL energy is reduced by 0.27 eV to 1841.29 eV.None of the shifts previously reported are affected by this readjustment but the absolute extra-atomic relaxation values derived previously via the Auger parameter are affected. Revision of R^ea_s values for phosphorus downward by 0.3 eV and sulfur values upward by 0.48 eV improves the agreement between the two series. New values are tabulated. The magnitude of relativistic curvature corrections required for various excitation and calibration situations for the non-retarding hemispherical sector analyzer is given.     

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.     

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.     

团簇碰撞中的相对转动研究

采用距离相关紧密束缚的分子动力学模型,研究了在不同碰撞能量以及不同的碰撞参数下,碱金属团簇碰撞过程中的转动行为.研究表明,团簇碰撞中存在着较大的转动.对确定的能量,存在极值的碰撞参数,小于该碰撞参数时,转动能量随碰撞参数增加而迅速增加;大于该碰撞参数时,转动能量随碰撞参数的增加迅速减小.能量低时,相对转动弛豫时间更长;碰撞能量越大,越过势垒的能力越强,势场的相对影响就越小,由此引起的相对转动也就越小.     

Auger parameter of hafnium in elemental hafnium and in hafnium oxide

X-ray photoelectron spectroscopy has been used to determine the Auger parameters in elemental hafnium and in hafnium oxide (HfO₂). The zirconium L_α line has been used as a source of excitation to study the 3d core levels of hafnium, the 1s core level of oxygen, and the X-ray excited MNN Auger region of hafnium and KVV Auger region of oxygen. The Auger parameters for hafnium and oxygen have been determined from these spectral data. In case of oxygen, the Auger parameter has been compared with the corresponding value in water. The change in the Auger parameter is observed to be negative for hafnium and positive for oxygen. We have shown that the opposite signs of the Auger parameters in binary systems can be utilized to determine the direction of charge transfer between the constituents. This is consistent with the chemical shift due to charge transfer. This chemical shift in the core level has been evaluated by subtracting the relaxation shift from the experimentally observed core level shift. It is found to be positive for the 3d_5/2 core level of hafnium in the oxide indicating a charge transfer from hafnium to oxygen in the oxide. The observations are consistent with Pauling’s electronegativity criterion.     

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.