AVS 46th International Symposium
    Applied Surface Science Division Tuesday Sessions
       Session AS-TuP

Paper AS-TuP15
Core-level Satellites and Outer Core-level Multiplet Splitting In Mn Model Compounds

Tuesday, October 26, 1999, 5:30 pm, Room 4C

Session: Poster Session
Presenter: A.J. Nelson, Lawrence Livermore National Laboratory
Authors: A.J. Nelson, Lawrence Livermore National Laboratory
J.G. Reynolds, Lawrence Livermore National Laboratory
J.W. Roos, Ethyl Petroleum Additives
Correspondent: Click to Email
We report a systematic study of the 2p, 3s and 3p core-level photoemission, satellite structures and valence bands of Mn model compounds. Charge-transfer from the ligand state to the 3d metal state is observed and is distinguished by the prominent shake-up satellite about 5 eV higher than the Mn 2p@sub 3/2@ peak for of all the Mn@super +2@ species and MnPO@sub 4@. The Mn 3s final state configuration can be either 3s3d@super 5@ or 3s3d@super 6@L depending on final state screening effects due to the ligand. We observe that the Mn 3s multiplet splitting becomes smaller as the Mn oxidation state increases, except for the Mn-phosphate species. Also, the 3s final state has @super 7@S and @super 5@S symmetry. In the @super 7@S state, the remaining 3s electron is well correlated with 3d electrons of parallel spin, while in the @super 5@S state the two spins are antiparallel. This electron correlation reduces the branching ratio of the @super 7@S:@super 5@S states as experimentally observed. In addition, as the ligand electronegativity decreases, the spin state purity is lost in the 3s spectra and the spectra becomes representative of mixed unscreened (3d@super N@) and locally screened (3d@super N+1@) final states. Our results are best understood in terms of configuration-interaction (CI) calculations including intrashell electron correlation, charge-transfer and final-state screening.