Theory of X-Ray Photoemission and X-Ray Emission Spectra in Mn Compounds

Ligand-field effects for the3pphotoelectron spectra ofCr2O3Bagus1, Ilton2, Rustad3 2004Phys. Rev. B171150View full textAdd to dashboardCite

“…[10][11][12] However, inter-atomic effects also contribute to the XPS. 6,[13][14][15][16][17][18][19][20][21] In this paper, we identify and establish the importance of condensed phase physical mechanisms that have not been explicitly related to XPS spectra in previous work based either on ab initio 4,13 or on parametrized, model Hamiltonian 14,17,18,21 cluster model studies. These mechanisms involve the ligand field splittings of the TM d shell and the covalent, bonding and antibonding, mixing of TM d and ligand p orbitals.…”

“…The crystal field splitting of the d-levels is well known. 22 Semi-empirical cluster model studies of the XPS of TM complexes have included parameters to represent this crystal field splitting; 2͑a͒, 17,18,21 one of these studies 21 was for the Cr 2p and 3p XPS of Cr 2 O 3 . However, to our knowledge, the direct connection of the lowering of the spatial degeneracy of the TM cation to the character of the XPS spectra has not been addressed previously.…”

“…It is often described in terms of configurations where there is no CT, d n , or where there is full CT, d nϩ1 L គ , where L គ indicates a ligand hole. 6,[17][18][19][20][21] The final, core-hole, state WF's are written as mixtures of d n and d nϩ1 L គ configurations; [13][14][15]17,18,21 although, in extreme cases, the final states are considered to be entirely d n or d nϩ1 L គ . 19,20 In this theoretical formulation, the d orbital is considered as a pure metal orbital and the L is considered as a pure ligand hole.…”

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

“…[8][9][10][11] Taguchi et al calculated the 3p photoemission spectra ͑XPS͒, the K␤ fluorescence emission ͑XES͒, and the spin-dependent 1s absorption spectra of different Mn compounds by means of an MX 6 cluster model including three configurations. 12,13 They treated the K␤ emission as a coherent second-order optical process and emphasized the influence of the core-hole potential on the 1s excitation spectra. Kawai et al analyzed the charge-transfer effect on the linewidth of Fe K␣ lines using a spinunrestricted DV-X␣ molecular-orbital calculation.…”

X-ray photoelectron spectroscopy study of electron and spatial structure of mono- and binuclear Ni(II) carboxylate complexes with nitrogen-containing ligands

“…Now, however, these are not single components but groups of component that have a rather complicated structure due to combined nonspherical electrostatic 3p-3d interaction and the spin-orbit interaction in the 3p-subshell. Additional important feature of the 3p-spectra is that the natural width of their components may vary within very broad limits, differing dozens of times for various 3p 5 d N ( 2S+1 L J ) components [19,20]. This leads to difficulties in comparing theoretical and experimental spectra.…”