Origin of the complex main and satellite features in Fe 2p XPS of Fe2O3.

Although the origin and assignment of the complex XPS features of the cations in ionic compounds has been the subject of extensive theoretical work, agreement with experimental observations remains insufficient for unambiguous interpretation. This paper presents a rigorous ab initio treatment of the main and satellite features in the Fe 2p XPS of Fe2O3. This has been possible using a unique methodology for the selection of orbitals that are used to form the ionic wavefunctions. This orbital selection makes it possible to treat both the angular momentum coupling of the open shell core and valence electrons as well the shake excitations from the closed shell orbitals associated with the O ligands into the valence open shell orbitals associated with the Fe 3d shell. This allows the character of the ionic states in terms of the occupations of the open shell core and valence orbitals and of the contributions of 2p1/2 and 2p3/2 ionization to the XPS intensities to be determined. Our analysis gives strong evidence that many body effects are essential for a correct description of the ionic states and, in general the states cannot be described by a single configuration over the open shell orbitals. An important consequence is that the Fe 2p XPS intensity in most of the features arises from small contributions from the ionization to many, tens to hundreds, of often unresolved ionic states. While the usual understanding of the lower binding energy main and satellite features as being dominantly from 2p3/2 ionization is confirmed, this is not the case for the higher binding energy features where 2p1/2 and 2p3/2 ionization and shake excitations in the valence space mix strongly. Furthermore, we have been able to show that a very large fraction, 88%, of the total Fe 2p XPS intensity is contained in a relatively small binding energy range of ∼35 eV. This is relevant if one wants to extract the stoichiometry of Fe2O3 from Fe 2p/O 1s intensity ratios. Similar considerations about the importance of many-body effects are likely to be relevant for other ionic compounds as well.

Combined multiplet theory and experiment for the Fe 2p and 3p XPS of FeO and Fe2O3.

The Al K alpha, 1486.6 eV, based x-ray photoelectron spectroscopy (XPS) of Fe 2p and Fe 3p for Fe(III) in Fe2O3 and Fe(II) in FeO is compared with theoretical predictions based on ab initio wavefunctions that accurately treat the final, core-hole, multiplets. The principal objectives of this comparison are to understand the multiplet structure and to evaluate the use of both the 2p and 3p spectra in determining oxidation states. In order to properly interpret the features of these spectra and to use the XPS to provide atomistic insights as well as atomic composition, it is necessary to understand the origin of the multiplet energies and intensities. The theoretical treatment takes into account the ligand field and spin-orbit splittings, the covalent mixing of ligand and Fe 3d orbitals, and the angular momentum coupling of the open shell electrons. These effects lead to the distribution of XPS intensity into a large number of final, ionic, states that are only partly resolved with energies spread over a wide range of binding energies. For this reason, it is necessary to record the Fe 2p and 3p XPS spectra over a wide energy range, which includes all the multiplets in the theoretical treatment as well as additional shake satellites. We also evaluate the effects of differing assumptions concerning the extrinsic background subtraction, to make sure our experimental spectrum may be fairly compared to the theory. We conclude that the Fe 3p XPS provides an additional means for distinguishing Fe(III) and Fe(II) oxidation states beyond just using the Fe 2p spectrum. In particular, with the use of the Fe 3p XPS, the depth of the material probed is about 1.5 times greater than for the Fe 2p XPS. In addition, a new type of atomic many-body effect that involves excitations into orbitals that have Fe f,ℓ = 3, symmetry has been shown to be important for the Fe 3p XPS.

Covalency in Fe2O3 and FeO: Consequences for XPS satellite intensity.

The covalent character of the interaction between the metal cation and the oxygen ligands has been examined for two Fe oxides with different nominal oxidation states, Fe(II)O, and Fe(III)2O3. The covalent character is examined for the initial, ground state configuration and for the ionic states involving the removal of a shallow core, Fe 3p, and a deep core, Fe 2p, electron. The covalency is assessed based on novel theoretical analyses of wave functions for the various cases. It is found that the covalency is considerably different for different oxidation states and for different ionized and non-ionized configurations. The changes in covalency for the ions are shown to be responsible for important changes in relaxation energies for X-Ray Photoelectron Spectroscopy (XPS) spectra and in the intensity lost from main XPS peaks to shake satellites. While these consequences are not observables themselves, they are important for the interpretation of the XPS spectra, in particular, for efforts to extract stoichiometries of these iron oxides from XPS data. This is a finding likely applicable across various 3d transition metal oxide materials.

Analysis of the Fe 2p XPS for hematite α Fe2O3: Consequences of covalent bonding and orbital splittings on multiplet splittings.

The origins of the complex Fe 2p X-Ray Photoelectron Spectra (XPS) of hematite (α-Fe2O3) are analyzed and related to the character of the bonding in this compound. This analysis provides a new and novel view of the reasons for XPS binding energies (BEs) and BE shifts, which deepens the current understanding and interpretation of the physical and chemical significance of the XPS. In particular, many-body effects are considered for the initial and the final, 2p-hole configuration wavefunctions. It is shown that a one-body or one-configuration analysis is not sufficient and that the many-body, many-determinantal, and many-configurational character of the wavefunctions must be taken into account to describe and understand why the XPS intensity is spread over an extremely large number of final 2p-hole multiplets. The focus is on the consequences of angular momentum coupling of the core and valence open shell electrons, the ligand field splittings of the valence shell orbitals, and the degree of covalent mixing of the Fe(3d) electrons with the O(2p) electrons. Novel theoretical methods are used to estimate the importance of these various terms. An important consequence of covalency is a reduction in the energy separation of the multiplets. Although shake satellites are not considered explicitly, the total losses of intensity from the angular momentum multiplets to shake satellites is determined and related to the covalent character of the Fe-O interaction. The losses are found to be the same for Fe 2p1/2 and 2p3/2 ionization.