Energy dependence of the outer core-level multiplet structures in atomic Mn and Mn-containing compounds

Hermsmeier, B.; Fadley, C. S.; Sinković, B.; Krause, Michael; Jiménez-Mier, J.; Gérard, Patrick; Carlson, T. A.; Manson, S. T.; Bhattacharya, SK

doi:10.1103/physrevb.48.12425

Cited by 66 publications

(48 citation statements)

References 51 publications

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“…Our analysis supports their interpretation and provides a quantitative understanding of differences and similarities between the XPS for the isolated atom and for MnO; we apply this analysis to examine aspects of the data in Hermsmeier et al 30 The first XPS peak appears to have a very similar FWHM for Mn gas, MnF 2 , and MnO, consistent, as we argued above, with the origin of this peak as a spin-orbit-split Russell-Saunders 7 P, multiplet. If the small broadening of this peak for MnO 6 over that for Mn 2+ , which we have ascribed to additional splittings in the O h * double group, were also found in their MnF 2 and MnO spectra, this would lend strong support to our analysis.…”

Section: Mn͑2+͒supporting

confidence: 83%

“…For Mn gas, peak 2 is a separate peak at 3.1 eV from the main peak, while from our calculations for isolated Mn 2+ , the separation of the centers of peaks 1 and 2 is ⌬E = 3.9 eV. As we explained above, our ⌬E is too large because we have not correctly described the separations of the 3d 5 muliplet couplings to 6 S, 4 P, and 4 P. However, Hermsmeier et al 30 find that this ⌬E becomes smaller for the compounds; it remains a separate peak for MnF 2 but it is only a shoulder on peak 1 for MnO. We have shown that ⌬E is reduced from the cation to MnO because the covalent character of the d orbitals leads to a smaller exchange integral, K͑3p ,3d͒; see Table II.…”

Section: Mn͑2+͒mentioning

confidence: 63%

“…Hermsmeier et al 30 showed that the Mn 3p XPS for Mn ͑gas͒, MnF 2 , and MnO are similar; they concluded that atomic effects dominate for the Mn XPS. Our analysis supports their interpretation and provides a quantitative understanding of differences and similarities between the XPS for the isolated atom and for MnO; we apply this analysis to examine aspects of the data in Hermsmeier et al 30 The first XPS peak appears to have a very similar FWHM for Mn gas, MnF 2 , and MnO, consistent, as we argued above, with the origin of this peak as a spin-orbit-split Russell-Saunders 7 P, multiplet.…”

Section: Mn͑2+͒mentioning

confidence: 99%

“…The relative XPS energies E rel of the different core-hole states are obtained directly from relativistic CI calculations. The relative XPS intensities I rel are determined using the sudden approximation 28,29 ͑SA͒; the SA is exact in the limit of high photon energies 28 and it is appropriate to use 30 for comparing our theoretical results with the XPS measurements of Ref. 1.…”

Section: Introductionmentioning

confidence: 99%

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Effects of covalency on thep-shell photoemission of transition metals:MnO

Bagus

Ilton

2006

Phys. Rev. B

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The effect of the solid-state environment for an Mn cation in MnO on the Mn 2p-and 3p-shell x-ray photoemission spectra ͑XPS͒ has been investigated using ab initio relativistic wave functions for an embedded MnO 6 cluster model of MnO. These wave functions include many-body effects due to the angular momentum coupling and recoupling of the open-shell electrons. They also include the covalent mixing of the metal d orbitals with ligand p orbitals. The treatment of covalency has not been included previously in ab initio theoretical studies of the 2p-shell XPS of transition-metal complexes. In this work, covalent interactions between the metal and ligands are treated on an equal footing with spin-orbit splittings. The four-component spinors used in these wave functions are optimized separately for the ground and for the 2p-and 3p-hole configurations. This orbital relaxation leads to a "closed-shell" interatomic screening of the Mn core hole. The different orbital sets optimized for the ground and core-ionized configurations mean that mutually nonorthogonal orbital sets are used to determine the matrix elements for the XPS relative intensities. Our treatment of the transition intensities is rigorous, and no approximations are introduced to handle the orbital nonorthogonality. The closed-shell screening is important because changes in the XPS obtained for the MnO 6 cluster from that obtained for an isolated Mn 2+ cation can be directly linked to this screening and to the consequent reduction in the values of certain exchange integrals. The present work is compared to prior, semiempirical calculations; these comparisons allow us to identify unresolved questions about the origin of certain features of the MnO XPS and to suggest further calculations to resolve these questions.

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Section: Mn͑2+͒supporting

confidence: 83%

Section: Mn͑2+͒mentioning

confidence: 63%

Section: Mn͑2+͒mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Effects of covalency on thep-shell photoemission of transition metals:MnO

Bagus

Ilton

2006

Phys. Rev. B

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“…Previous photoemission studies on transition metal compounds reveal core-level multiplet structures that are best understood in terms of configuration-interaction (CI) calculations including intrashell electron correlation, charge-transfer and final-state screening. [3][4][5] In addition, these multiplet structures are also strongly influenced by covalency and ligand coordination. [6,7] The This paper presents the results of a systematic study of the 3s and 3p core-level photoemission, and satellite structures for Mn oxo-bridged compounds.…”

Section: Introductionmentioning

confidence: 99%

High Spin Mn Molecular Clusters: Spin State Effects On the Outer Core-Level Multiplet Structures

2001

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Oxo-bridged manganese polynuclear complexes have applications in a variety of technologies, such as single-molecule nanomagnets, catalysis and photosynthetic redox chemistry. The reason that these types of compounds are capable of such important and varied technologies is thought to be because they possess ground states with large spin values. However, the electronic, structural and magnetochemical relationships are not well understood and need to be thoroughly investigated to adequately explain why Mn is such an integral part of so many useful processes. X-ray photoemission spectroscopy was used to study the Mn 3p, 3s and valence band electronic behavior as a function of Mn cluster structural properties, where the cluster size and nuclearity are systematically varied. Results show a chemical shift of the Mn 3 p3/2,1/2 spin-orbit pair related to the cluster size and nuclearity. Also, the Mn 3s 7 S and 5S final state multiplet components shift since it involves the binding energy of a ligand valence electron. In addition, the branching ratio of the 78158 states is related to the 3s 3d electron correlation. Specifically, in the 7S state, the remaining 3s electron is well correlated with 3d electrons of parallel spin, while in the 5S state the two spins are antiparallel. Changes in this electron correlation are clearly observed in the 7 S.S branching ratio as a function of cluster size and ligand electronegativity.

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Pt/MnO Interface Induced Defects for High Reverse Water Gas Shift Activity

Szenti,

Efremova,

Kiss

et al. 2024

Angewandte Chemie

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The implementation of supported metal catalysts heavily relies on the synergistic interactions between metal nanoparticles and the material they are dispersed on. It is clear that interfacial perimeter sites have outstanding skills for turning catalytic reactions over, however, high activity and selectivity of the designed interface‐induced metal distortion can also obtain catalysts for the most crucial industrial processes as evidenced in this paper. Herein, the beneficial synergy established between designed Pt nanoparticles and MnO in the course of the reverse water gas shift (RWGS) reaction resulted in a Pt/MnO catalyst having ~10 times higher activity compared to the reference Pt/SBA‐15 catalyst with >99% CO selectivity. Under activation, a crystal assembly through the metallic Pt (110) and MnO evolved, where the plane distance differences caused a mismatched row structure in softer Pt nanoparticles, which was identified by microscopic and surface‐sensitive spectroscopic characterizations combined with density functional theory simulations. The generated edge dislocations caused the Pt lattice expansion which led to the weakening of the Pt‐CO bond. Even though MnO also exhibited an adverse effect on Pt by lowering the number of exposed metal sites, rapid desorption of the linearly adsorbed CO species governed the performance of the Pt/MnO in the RWGS.

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Energy dependence of the outer core-level multiplet structures in atomic Mn and Mn-containing compounds

Cited by 66 publications

References 51 publications

Effects of covalency on thep-shell photoemission of transition metals:MnO

Effects of covalency on thep-shell photoemission of transition metals:MnO

High Spin Mn Molecular Clusters: Spin State Effects On the Outer Core-Level Multiplet Structures

Pt/MnO Interface Induced Defects for High Reverse Water Gas Shift Activity

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