Characterization of charge transfer excitations in hexacyanomanganate(III) with Mn K-edge resonant inelastic x-ray scattering

Journal Article · Wed Apr 07 00:00:00 EDT 2010 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3367958· OSTI ID:21559851

Meyer, Drew A ^[1]; Xuena, Zhang; Gaffney, Kelly J ^[2]; Bergmann, Uwe ^[3]

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1. Department of Chemistry, Stanford University, 333 Campus Drive, Stanford, California 94305-5080 (United States)
2. PULSE Institute for Ultrafast Energy Science, SLAC National Accelerator Laboratory, Stanford University, Stanford, California 94305 (United States)
3. Linac Coherent Light Source, SLAC National Accelerator Laboratory, Stanford University, Stanford, California 94305 (United States)

We use hard x-ray resonant inelastic x-ray scattering (RIXS) and density functional theory (DFT) calculations to characterize charge transfer excitations in K{sub 3}Mn(CN){sub 6}. The combination of RIXS measurements and DFT calculations allows us to characterize the strength of the ligand-metal electronic interaction and assign the Raman resonances in the RIXS spectra to charge transfer excitations. With x-ray excitation energies resonant with the T{sub 2g} and E{sub g} pre-edge peaks derived predominantly from the Mn 3d orbitals, we observe Raman resonances in the energy transfer range from 2 to 12 eV, which results from the filling of the 1s core-hole from T{sub 1u}-symmetry occupied orbitals. DFT calculations indicate that these orbitals exhibit primarily ligand character, supporting the assignment of the energy transfer resonances to ligand-to-metal charge transfer excitations. Our RIXS measurements and DFT calculations also indicate that the E{sub g}-orbital spin-splits by roughly 0.8 eV, though we do not cleanly resolve the two absorption peaks in the RIXS spectra. We also see evidence for a metal-to-ligand charge transfer (MLCT) excitation when exciting with a 6545.0 eV incident photon, roughly 4 eV above the E{sub g} absorption peaks. The 6545.0 eV resonant emission spectrum shows a 6.0 eV energy transfer resonance, which corresponds to a final state hole in the T{sub 2g} partially occupied orbital. DFT calculations indicate that excitation at 6545.0 eV populates an unoccupied T{sub 1u}-symmetry orbital of primarily ligand character. Given the predominantly metal character of the final state hole, we assign the 6.0 eV Raman resonance to a MLCT excitation. These measurements demonstrate the ability of hard x-ray RIXS to characterize the valence electronic structure of coordination compounds.

• OSTI ID: 21559851
• Journal Information: Journal of Chemical Physics, Vol. 132, Issue 13; Other Information: DOI: 10.1063/1.3367958; (c) 2010 American Institute of Physics; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ABSORPTION
ABSORPTION SPECTROSCOPY
DENSITY FUNCTIONAL METHOD
ELECTRONIC STRUCTURE
EMISSION SPECTRA
ENERGY TRANSFER
EV RANGE
EXCITATION
HARD X RADIATION
HOLES
LIGANDS
MANGANESE COMPOUNDS
METALS
PEAKS
PHOTONS
POTASSIUM COMPOUNDS
RAMAN SPECTRA
RESONANCE
X-RAY DIFFRACTION
X-RAY SPECTROSCOPY
ALKALI METAL COMPOUNDS
BOSONS
CALCULATION METHODS
COHERENT SCATTERING
DIFFRACTION
ELECTROMAGNETIC RADIATION
ELEMENTARY PARTICLES
ELEMENTS
ENERGY RANGE
ENERGY-LEVEL TRANSITIONS
IONIZING RADIATIONS
MASSLESS PARTICLES
RADIATIONS
SCATTERING
SORPTION
SPECTRA
SPECTROSCOPY
TRANSITION ELEMENT COMPOUNDS
VARIATIONAL METHODS
X RADIATION