An X-ray photoelectron spectroscopic study of some nickel (II) amine complexes

The X-ray photoelectron (XPS) spectra of several Ni(II) diamine complexes, a Ni(II) triamine complex and several Ni(II) diimine complexes are reported in terms of the Ni 2p, Cl 2p and N 1s core level binding energies. Theoretical models are presented to account for the quadratic relationship observed between XPS Ni 2p_{$\text{3}\text{2}$}binding energy shifts and the N-H infrared rocking frequency as related to these complexes. On the basis of this correlation, it is possible to discriminate between free counter-ions coordinated to the metal or involved in cluster-ion formation. Individual XPS data for these complexes are interpreted in terms of the intrinsic nature of the metal environment and an attempt is made to calculate the metal and donor nitrogen atomic charges for selected complexes.     

(II) Infrared and X-ray photoelectron spectroscopy of some transition metal dithiocarbamates and xanthates

Measurements are presented for the binding energy variations of (a) (Ni, Cu) 2p_{$\text{3}\text{2}$}, S 2p and N 1s core levels in a series of Ni and Cu disubstituted dithiocarbamates and (b) (Ni, Cu) 2p_{$\text{3}\text{2}$}, and S 2p core levels in a series of Ni xanthates. These shifts, which are observed to be negative and quite large for the S 2p levels, are then correlated with the infrared absorption frequency variations for the associated intramolecular stretching vibrations of the same series. The results are interpreted in terms of a model based on atomic charges and their potential effects on both variations. The functional relationships between the binding energy and infrared frequency variations are shown to be in good agreement with the experimental results.     

The effects of the lithium intercalation on the X-ray photoelectron spectra of NiPS3

Summary A detailed XPS study of the lithium-intercalated NiPS₃ specimens was performed at the 2p, 3p, 3s core levels of the nickel atoms and at the 2p core levels of the sulphur and phosphorous atoms for various lithium contents. Comparison of the Ni 2p, 3p and 3s XPS spectra corresponding to NiPS₃ and Li _x NiPS₃ systems shows some evident trends. In particular, a shift of the Ni main line towards lower binding energies, a decrease in the intensity of the Ni 3p, 2p satellite structures and a change in the full width at half maximum of the Ni 3s band with lithium content are observed. All these findings suggest a change in the 3d electron configuration for high lithium concentrations. As regards the cluster (P₂S₆)⁴⁻, with the addition of lithium, a P 2p main line shift towards higher binding energies is noted, while the S 2p peak shifts towards lower binding energies. These results are discussed in comparison with previous physical measurements concerning the nickel reduction process and the related electronic modifications. The authors of this paper have agreed to not receive the proofs for correction.     

Accurate core binding energies of ions from Dirac-Fock calculations combined with experimental atomic binding energies

Core binding energies are reported for the singly-charged alkali ions obtained by removing the outer s electron and for the singly-charged halide ions obtained by adding a P_{$\text{3}\text{2}$} electron. The levels studied are Li 1s, Na 1s, K 2p, Rb 3p, Cs 3d, F 1s, Cl 2p, Br 3p and I 3d. The binding energies were obtained by combining DiracF?ock ΔSCF binding-energy shifts between the ions and the corresponding isoelectronic rare gases with experimental rare-gas binding energies, and also by combining the calculated atomīon shifts with experimental atomic binding energies where available. It is shown that the former approach corrects accurately for the correlation energy, which is not included in single-configuration calculations.     

X-Ray photoelectron spectrum of methylisocyanide gas

The C and N 1s spectra of methylisocyanide gas have been recorded. Two resolvable peaks of equal intensity are observed in the C 1s spectrum. Using the equivalent-cores approximation and thermochemical data, together with MNDO MO calculations and the point-charge potential model, the lower-binding-energy C 1s line is assigned to photo-emission from the isocyano carbon. The strong satellites which have been observed in the spectra of coordination complexes of alkyl and aryl isocyanides are not observed in the spectra of the free molecule. Comparisons of the point-charge-potential-corrected binding energies for C 1s and N 1s photoemissions from CH₃NC and its isomer CH₃CN with those for a host of other molecules show that photoemissions from the internal atoms in these molecules are accompanied by substantially less than average relaxation energies. These smaller relaxation energies can be understood using valence-bond theory.     

An ESCA investigation of some thiocyanato complexes

A series of simple thiocyanato complex ions have been investigated as their tetraphenylphosphonium and potassium salts. The binding energies of N, C and S were determined as well as those of the metals. From the first-mentioned data effective charge-values were estimated for the atoms of the ligands. For this purpose linear relations E_b = kq + E_b0 were used that had been previously established within a scheme having C_1s (phenyl) as the internal standard.From the data thus obtained the effective charge on the metal atoms was estimated. For elements where we have sufficient data the same type of linear relation seems to he followed. Tentatively valid examples are E_b(Ni) = 6.74q_Ni + 848.3 eV and E_b(Pd) = 4.45q_Pd + 333.9 eV.In this interpretation the atoms of the metals are considered to be positively charged and surrounded by the negative charge of the electrons occupying the s band.It is further suggested for complexes with pronounced π backbonding (Pt(SCN)₄^2?, Pd(SCN)₄^2? and Hg(SCN)₄^2?) that the C 1s binding energy measured for the carbon atom of the SCN^? ligand is composed of the ionisation energy from the 1s level and an additional term corresponding to the intraligand π → π* transition.     

Characterization of plasma polymer films of phenylsilane by X-ray photoelectron spectroscopy

Carbon 1s and silicon 2p X-ray photoelectron spectra of phenylsilane plasma polymer films prepared at substrate temperatures,T_s, between 50 and 450°C were recorded. The binding energies, lineshapes, and shake-up satellite intensities are in accordance with a structure consisting of a silicon network with pendant phenyl groups, and the minor dependence on T_s is consistent with the main effect of increasing preparation temperature being the loss of hydrogen and some pendant phenyl, with a concurrent increase in the interconnectivity of the network. The observed C 1s binding energy and linewidth specifically rule out the presence of any significant amount of carbon in silicon carbide form. A simultaneous shift of about 0.6 eV in the binding energies of both the C 1s and Si 2p lines is tentatively interpreted as a shift in the Fermi level with respect to the valence band edge.     

Shell-model calculations on Ni and Cu isotopes

Binding energies, excitation energies and spectroscopic factors have been calculated for^57–67Ni and^58–68Cu in an unrestricted (2p_3/2, lf _5/2,2p_1/2) shell-model space. The effective two-body matrix elements are obtained from the modified surface delta interaction (MSDI) and from a least-squares fit to experimental binding and excitation energies (ASDI). The average deviation between about 100 experimental and calculated energies is 0.14MeV for MSDI and 0.08 MeV for ASDI. Excitation energies of high-spin states are given also. Spectroscopic factors have been calculated for all single-nucleon transfer reactions on stable Ni or Cu targets leading to Ni or Cu isotopes. For spectroscopic factors larger than 0.4 the average deviation between theory and experiment is about 30%. The experimentally observed and calculated spectroscopic strengths are compared by using sum rules and are found to be consistent. An extensive compilation has been made of experimental data on energies,J ^π assignments and spectroscopic factors.     

A study of SO2 adsorption on CaO (100) surfaces using X-ray photoelectron spectroscopy

The adsorption of SO₂ on CaO (100) at 300 K has been studied using X-ray photoelectron spectroscopy. Under ultrahigh-vacuum conditions, the surface was exposed to 0–500 Langmuirs of SO₂. The resulting adsorption yields a single SO surface species with an S 2p peak at 168.2 eV and an O 1s_{$\text{sol1}\text{2}$} peak at 531.7 eV. Subsequent heating of the exposed surface to 673 K indicated no desorption or changes in the binding energies of the S 2p and O 1s_{$\text{1}\text{2}$} peaks. On the basis of these data and binding-energy data for standard compounds, the adsorbed species is identified as SO₄^2?. The surface coverage due to the SO₄^2? species was also measured as a function of SO₂ exposure. From these data, the initial adsorption is found to be first-order in surface coverage, and the initial sticking probability is found to have a value of 0.4.     

Development of electronic structure of Ni thin films on Cu(0 0 1) surfaces

We have traced the development of the Ni electronic structure with thickness variation on flat and nano-structured Cu(0 0 1) surfaces by means of photoemission spectroscopy. The binding energy of the Ni 2p_3/2 main peak and satellite peak is found to have shifted monotonically in the direction opposite to each other, with the increase of Ni coverage. The reduced binding energy of the thin film’s main peak is strongly correlated to the Cu 4s/Ni 3d interfacial hybridization effect (s/d IHE) and the narrowing of the d band with the reduction of dimensions, while the increased satellite binding energy results from the combination of interface hybridization and expansion of an extended 4s-like state towards the vacuum. The center of the Ni d_xy band is predicted to shift closer to the Fermi level with increasing film thickness. Enhanced satellite intensity in thin films is observed, correlating to the narrowing of the d band with decreased film thickness. Through comparison of Ni films grown on flat versus nano-structured Cu(0 0 1) surfaces, the mixing of Cu and Ni atoms is found to be enhanced at the terrace edge region and consequently a larger s/d IHE is predicted for Ni on the nano-structured surface.     

An ESCA investigation of some copper complexes

A series of copper complexes have been investigated by ESCA. All complexes were salts of the tetraphenylphosphonium ion. The binding energies of all the atoms in the complexes were determined. From the binding energies of the ligand atoms we estimated the effective charges on these atoms. For this purpose we used linear relations of the formE_b = kq + E_bO which had been established previously within our scheme of C 1s (phenyl) as internal standard. From the data thus obtained, the effective charge on the copper atom was estimated. A linear relation between binding energy and the effective charge on the copper atom was found, i.e.,E_b(Cu) = 1.52q_Cu + 932.2ESCA spectra were recorded for the complexes bis(1,3-diphenyl-1,3-propanediono) copper (II) and bis(3-phenyl-2,4-pentanediono) copper (II). By a combination of the XPS binding energies and IR intensities of the ν_CH vibrations of the phenyl groups in the complexes with empirical relations between these entities and the effective charges of the atoms and groups, a fairly complete mapping of the charge distributions of these complexes has been achieved.     

Correlation of inner shell binding energies with shifts of charge transfer bands

Inner shell binding energies were determined for the elements in the crystalline compounds A^IIIX^VO₄ where A  B, Al, Ga, Fe and X  P, As with fourfold coordination of A, and in the corresponding dihydrates of Al having a sixfold coordination of Al. The O 1s binding energies for the dihydrates could be resolved into two bands arising from XO₄ -groups and from the water molecules respectively. The O 1s binding energies from the XO₄ groups decrease by about 0.6 eV in going from the anhydrous compounds to their dihydrates whereas the Al 2p binding energies remain constant within the limits of error. These results correlate surprisingly well with shifts of the first charge transfer band of trivalent iron in these compounds. The binding energy differences between phosphates and arsenates are also in good agreement with concurrent shifts of this charge transfer band. The consequences of these results for the concept of optical electronegativities are discussed.     

Binding energies of hypernuclei and ΛN interaction

A central ΛN potential V _ΛN is found on the basis of an analysis of the binding energies of 1s-shell hypernuclei and Λp scattering. Within the exprerimental errors, this potential makes it possible to reproduce the binding energies of three-, four-, and five-particle ground and excited states of hypernuclei and the angular and energy dependences of the cross sections for Λp scattering. The accuracy and reliability of the calculation of three-, four-, and five-particle hypernuclear and the respective nuclear systems is ensured by determining both upper and lower bounds on the energy. Within the Λ plus core model, the potential V _ΛN is matched with binding energies of heavy hypernuclei.     

Study of cross sections for the loss of outer 1s, 2s, and 2p electrons by fast ions and atoms of light elements

In the case of light-element ions propagating with velocities V = 1.83 and 3.65 au in H₂, He, N₂, Ne, and Ar, the loss cross sections σ_{i, i+m} for m electrons (m = 1, 2, 3) are considered. The partial loss cross sections σ_i(nl) for one of the outer 1s, 2s, or 2p electrons are determined using the obtained data. It is shown that the experimental cross sections for the loss of the 1s and 2s electrons by positive ions qualitatively agree with the theoretical values calculated in the Born approximation. In the case of the ion velocity V = 1.83 au, the cross sections σ_i for 2p electrons are greater than the cross sections σ_i (1s) and σ_i (2s) by a factor of 1.2–3 for the same binding energies of electrons in the ion (I _nl > 20 eV). It is found experimentally that, at V = 1.83 au, the cross sections σ_i (2p) for I _nl ～ 10–20 eV are less than the cross sections σ_i (1s) by a factor of 2–3, which is probably caused by a decrease in the screening parameter (θ_2p < 1) of the outer shell of atoms.     

Binding energies of hypernuclei and ΛN interaction

A central ΛN potential V _ΛN that describes, in the limits of experimental errors, the binding energies of three-, four-, and five-particle ground and excited states of hypernuclei, as well as energy and angular dependence of Λp scattering cross sections, is found on the basis of a conjoint analysis of binding energies of 1s-shell hypernuclei and Λp scattering. The reliability and accuracy of three-, four-, and five-particle calculations of hypernuclei and related nuclear systems are assured by the estimation of, an upper, as well as a lower bound of energy. In the framework of the model Λ+core, V _ΛN agrees with binding energies of heavy hypernuclei.     

Formation of doubly excited He atoms during scattering of He ions from a clean and oxygen covered Ni(1 1 0) surface

The formation of doubly excited states of He atoms during collisions of He²⁺ ions with energies between 60 eV and 1 keV with a Ni(1 1 0) surface is studied via Auger electron spectroscopy. We observe that the electron spectra from autoionization of doubly excited states of 2s², 2s2p, 2p² configurations show a pronounced dependence on the coverage of the target surface with oxygen. For a controlled O₂ adsorption on the Ni(1 1 0) surface we can explain the resulting changes in the electron spectra by the modification of the work function of the target surface. Thermal desorption and dissolution into the bulk of surface contaminations at elevated temperatures provides an alternative interpretation of recent work where the local electron spin polarization of a Ni(1 1 0) surface was deduced from changes in the electron spectra as function of target temperature.     

Oxidation of a cesium-covered Ni (1 1 0) surface studied by metastable-induced electron spectroscopy

An initial stage of oxidation of a cesium-covered Ni (1 1 0) surface has been studied by metastable-induced electron spectroscopy (MIES) and low-energy electron diffraction (LEED). The MIES brought spectra with Cs 6s induced peak (P_6s), Cs 5p (P_5p), O 2p induced peak (P_ox) and a structure related to the substrate Ni 3d states (P_3d). The work function change Δφ showed an oscillatory behavior in the progress of surface oxidation. The process is divided into three stages: (i) at low O₂ exposures, Δφ > 0 with unchanging P_5p and P_6s; (ii) at moderate exposures, Δφ < 0 with a drastic decrease in the P_6s intensity; (iii) at higher exposures, Δφ > 0 with shifts of peaks P_5p and P_ox to higher energies, together with an appearance of peak P_3d. A three-step model of initial oxidation of alkali-covered Ni (1 1 0) surfaces is presented.     

Heat of mixing in HfCxN1−x compounds from XPS core level binding energy shifts

The XPS core level binding energies for the Hf4f_{$\text{7}\text{2}$}, Cls and Nls level in several nearly stoichiometric HfC_xN_1?x compounds are reported. Using the thermochemical model to calculate core level binding energy shifts in metals the heat of mixing as function of the HfC/HfN ratio is calculated from the position of the Cls binding energies. In addition it is shown that the Hf4f_{$\text{7}\text{2}$} and Nls binding energies can be used to obtain further thermochemical data for these compounds.     

Relativistic core binding energies of selected atoms: Comparison with experiment and other calculations

Single-configuration Dirac—Fock binding energies are reported for K 2p, Rb 3p, Cs 3d, Mg 1s, Zn 2p, and Cd 3d as well as for the corresponding levels in the cations of these elements and the neighboring rare gases. The results are compared with similar Dirac—Slater and Hartree—Fock calculations, and with experiment. It is found that the calculated binding energies are generally in very good agreement with experiment and are superior to the Dirac—Slater and Hartree—Fock results. The relativistic contribution is shown to be significant even for lighter atoms.     

The effect of the next nearest neighbor ion on the X-ray photoelectron spectra of 2p levels for Co2+, Ni2+ and Cu2+ in MgO

The X-ray photoelectron spectra of Co, Ni and Cu 2p levels for samples of M_xMg_1-xO (M = Co, Ni, Cu), CoO, NiO and CuO were compared. The binding energies of metal 2p_{$\text{3}\text{2}$} levels did not change with their concentration. The shake-up satellite main peak intensity ratios and FWHM of metal 2p levels for Co²⁺ and Cu²⁺ in MgO were smaller than those for CoO and CuO. The Ni 2p_{$\text{3}\text{2}$} spectrum for Ni²⁺ in MgO had no shoulder, unlike NiO. Results indicate that next nearest neighbor ions (metal ions) may influence the final states after photoelectron ejection.