Multiplet Splitting of Core-Electron Binding Energies in Transition-Metal Ions

Fadley, C. S.; Shirley, D. A.; Freeman, Arthur J; Bagus, Paul S.; Mallow, Jeffry V.

doi:10.1103/physrevlett.23.1397

Cited by 304 publications

(119 citation statements)

References 12 publications

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“…In 3d transition metal compounds, a well separated satellite by spin-exchange interaction can only be seen for the 3s orbital. This is because the multiplet effect in the 3s spectrum is less prominent than in the other core-level spectra and the magnitude of the exchange integral between the 3d and each core-level is the largest for the 3s level [14,15,16]. Then, we also deconvoluted this small peak into two components corresponding to the Mn(1) and Mn(2) components by assuming a relative intensity of 2:3.…”

Section: Resultsmentioning

confidence: 99%

Bulk-sensitive photoemission of Mn5Si3

Irizawa

Yamasaki

Okazaki

et al. 2002

Solid State Communications

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We have carried out a bulk-sensitive high-resolution photoemission experiment on Mn 5 Si 3 . The measurements are performed for both core level and valence band states. The Mn core level spectra are deconvoluted into two components corresponding to different crystallographic sites. The asymmetry of each component is of noticeable magnitude. In contrast, the Si 2p spectrum shows a simple Lorentzian shape with low asymmetry. The peaks of the valence band spectrum correspond well to the peak positions predicted by the former band calculation.

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Section: Resultsmentioning

confidence: 99%

Bulk-sensitive photoemission of Mn5Si3

Irizawa

Yamasaki

Okazaki

et al. 2002

Solid State Communications

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“…This phenomenon is termed multiplet SJ>litting of core-level binding energies. It was first reported in molecules by Hedman~ ~~., 10 12 . It has since been studied in transition metal salts 13 -lB and in the valence-band spectra of metal~.…”

Section: This Technique Is Capable Of Yielding Binding Energiesmentioning

confidence: 96%

Multiplet splitting in 1s hole states of molecules

Davis

Martin

Banna

et al. 1973

The Journal of Chemical Physics

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The binding energies of selected C, N, O, and F 1s electrons in six paramagnetic molecules were measured by x-ray photoemission. A splitting of 1.934(41) eV was observed in the N(1s) line of NF2, and several other splittings were remeasured or obtained by fitting asymmetric but unresolved lines. Use of the Mg Kα12 doublet profile in fitting improved the fits markedly. A multiplet hole theory was developed to predict the final-state multiplet splitting. It uses atomic exchange integrals, INDO calculations on an ``equivalent-core'' final state to obtain spin densities, and Van Vleck's Theorem to account correctly for multiplicity. It gives results in very good agreement with experiment, and it can be used for larger molecules. During photoemission spin density migrates away from the 1s hole in most cases, and electronic charge flows toward this hole, affecting both the 1s splitting and the 1s binding energy. The lower N(1s) binding energy in di-t -butylnitroxide than in NO arises from electron flow to nitrogen from the t -butyl group during photoemission. This inductive effect is closely related to the ease of substitution of nucleophilic groups in unimolecular reactions with tertiary alkyl halides, a phenomenon that must also be understood in terms of final- (or transition-) state properties, rather than simply in terms of the initial state. Inequivalent fluorines in N2F4 were identified by an unresolved doublet structure in the F(1s) peak.

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“…These splittings are considerably reduced from free-ion predictions, and a major source of this reduction appears to be covalent-bondfng effects. 8 The 3p binding energies in these solids also give evidence for splittings, but from both a theoretical and experimental point of view, the interpretation of this data is less straightforward. 8…”

Section: This Is a Library Circulatingmentioning

confidence: 99%

“…8 • 9 Thus, the relative intensities obtained from frozen-orbital MHT calculations on Mn 3 + are: 5 P 1 , 0.66; 5 The P 2 peak would thus probably be too weak to observe. Spectra for MnF 2 in fact show two weaker components (3p(2) and 3p(3)) in addition to 3p(l).…”

Section: Ucrl-19566mentioning

confidence: 99%