SIMPLE CORRELATION BETWEEN MN-K-ALPHA X-RAY-EMISSION AND MN 2P X-RAY PHOTOELECTRON-SPECTRA FOR HIGH OXIDATION NUMBER OR LOW-SPIN MANGANESE COMPOUNDS

The high-resolution Mn-K alpha X-ray emission spectra (XES) and Mn 2p X-ray photoelectron spectra (XPS) for K[MnO4], K-3[Mn(CN)(5)(NO)], K-2 [MnO4] and K-3[Mn(CN)(6)] were measured. The first and second compound s which have no unpaired electrons, give symmetrical peaks in Mn-K alp ha(1), XES and Mn 2p(3/2) XPS spectra. The spectra of the other compou nds show asymmetrical lines. When the lines are divided into two Loren zian (for XES) or Gaussian (for XPS) curves, the energy separation and intensity ratio of the two peaks coincide with each other in both spe ctroscopies. These results are rationalized by spin-unrestricted DV-X alpha molecular-orbital calculations of the anions. The electronic str uctures of these anions are calculated for their ground state and hole states in 1s and 2p levels. It is concluded that the electronic struc tures of the compounds in the ground states are conserved in the core hole states. Thus the satellite peaks due to charge transfer are not o bserved and the peak profiles are governed by the exchange splitting b etween 2p and valence electrons.