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      Molecular Orbital Simulations of Metal 1s2p Resonant Inelastic X-ray Scattering.

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          Abstract

          For first-row transition metals, high-resolution 3d electronic structure information can be obtained using resonant inelastic X-ray scattering (RIXS). In the hard X-ray region, a K pre-edge (1s→3d) excitation can be followed by monitoring the dipole-allowed Kα (2p→1s) or Kβ (3p→1s) emission, processes labeled 1s2p or 1s3p RIXS. Here the restricted active space (RAS) approach, which is a molecular orbital method, is used for the first time to study hard X-ray RIXS processes. This is achieved by including the two sets of core orbitals in different partitions of the active space. Transition intensities are calculated using both first- and second-order expansions of the wave vector, including, but not limited to, electric dipoles and quadrupoles. The accuracy of the approach is tested for 1s2p RIXS of iron hexacyanides [Fe(CN)6](n-) in ferrous and ferric oxidation states. RAS simulations accurately describe the multiplet structures and the role of 2p and 3d spin-orbit coupling on energies and selection rules. Compared to experiment, relative energies of the two [Fe(CN)6](3-) resonances deviate by 0.2 eV in both incident energy and energy transfer directions, and multiplet splittings in [Fe(CN)6](4-) are reproduced within 0.1 eV. These values are similar to what can be expected for valence excitations. The development opens the modeling of hard X-ray scattering processes for both solution catalysts and enzymatic systems.

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          Author and article information

          Journal
          J Phys Chem A
          The journal of physical chemistry. A
          American Chemical Society (ACS)
          1520-5215
          1089-5639
          Jul 28 2016
          : 120
          : 29
          Affiliations
          [1 ] Department of Chemistry-Ångström Laboratory, Uppsala University , Box 538, SE-751 21 Uppsala, Sweden.
          Article
          10.1021/acs.jpca.6b05139
          27398775
          4f1bc584-aaaf-4af7-bef8-de079dfbefdc
          History

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