Suppression of the low-spin multiplet components in the3pphotoelectron spectra of atomic and solid3dmetals

Influence of the core hole onKβemission following photoionization or orbital electron capture: A comparison using MnO and55Fe2Glatzel1, Bergmann2, Groot3 et al. 2001Phys. Rev. B531340View full textAdd to dashboardCite

“…12 Calculations by several authors showed that the decay rates strongly depend on the multiplet term of the final state and they could successfully explain the suppression of the low-spin components in the 3p XPS of atomic Cr and Mn and in the K␤ spectra of Mn compounds. 12,15 For the latter, satisfactory agreement was achieved for MnO and MnF 2 between theory and experiment by assuming a linear relation (0.2 FWHM͒ between the final-state energy and the lifetime broadening of the final states. Hansen et al obtained 0.13 eV and 2.5 eV FWHM including CI for the 3p 5 3d 5 ( 6 S) 7 P and 5 P final states of atomic Mn, respectively.…”

“…It is interesting to note that Hansen calculated ab initio for Mn atoms that the 3d 6 ( 5 D)4s 6 D term shifts below the 3d 5 4s 2 6 S term when a 3p electron is removed. 15 This demonstrates the analogy between 4s to 3d shake-down processes in atoms and ligand-to-metal charge transfer in molecules and solids.…”

“…Hansen et al obtained 0.13 eV and 2.5 eV FWHM including CI for the 3p 5 3d 5 ( 6 S) 7 P and 5 P final states of atomic Mn, respectively. 15 They found a considerable decrease in the final state lifetime in CI calculations over single-configuration calculations for Mn atoms.…”

“…15,38 In atomic calculations, only the 4 D term shows considerable intensity. 15 Together, with the dipole selection rules for optical transitions one obtains ( 6 S) 5 P, ( 6 S) 7 P, and ( 4 D) 5 P for the final states, where the LS term in brackets refers to the symmetry in the 3d shell. The ( 6 S) 7 P and ( 6 S) 5 P terms are split by the strong (3p,3d) exchange interaction and spread over 15 eV.…”

“…Von dem Borne and collaborators performed 3p XPS mea-surements and calculations for atomic Mn including, among other configurations, 4s to 3d shake-down processes, which can be considered the atomic equivalent to ligand-to-metal charge transfer in solids and molecules. 15 They distinguish between weak and strong CI depending on the overlap between the interacting electrons. The former can be approximated by appropriate scaling of the direct and exchange Slater integrals, while the latter requires explicit inclusion of the strongly interacting configurations.…”