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@ARTICLE{Murphy:1029087,
      author       = {Murphy, Gabriel L. and Bazarkina, Elena and Svitlyk,
                      Volodymyr and Rossberg, André and Potts, Shannon and
                      Hennig, Christoph and Henkes, Maximilian and Kvashnina,
                      Kristina O. and Huittinen, Nina},
      title        = {{P}robing the {L}ong- and {S}hort-{R}ange {S}tructural
                      {C}hemistry in the {C}-{T}ype {B}ixbyite {O}xides {T}h 0.40
                      {N}d 0.48 {C}e 0.12 {O} 1.76 , {T}h 0.47 {N}d 0.43 {C}e 0.10
                      {O} 1.785 , and {T}h 0.45 {N}d 0.37 {C}e 0.18 {O} 1.815 via
                      {S}ynchrotron {X}-ray {D}iffraction and {A}bsorption
                      {S}pectroscopy},
      journal      = {ACS omega},
      volume       = {9},
      number       = {25},
      issn         = {2470-1343},
      address      = {Washington, DC},
      publisher    = {ACS Publications},
      reportid     = {FZJ-2024-04948},
      pages        = {27397 - 27406},
      year         = {2024},
      abstract     = {The long- and short-range structural chemistry of the
                      C-type bixbyite compounds Th0.40Nd0.48Ce0.12O1.76,
                      Th0.47Nd0.43Ce0.10O1.785, and Th0.45Nd0.37Ce0.18O1.815 is
                      systematically examined using synchrotron X-ray powder
                      diffraction (S-PXRD), high-energy resolution fluorescence
                      detection X-ray absorption near edge (HERFD-XANES), and
                      extended X-ray absorption fine structure spectroscopy
                      (EXAFS) measurements supported by electronic structure
                      calculations. S-PXRD measurements revealed that the title
                      compounds all form classical C-type bixbyite structures in
                      space group Ia3̅ that have disordered cationic
                      crystallographic sites with further observation of
                      characteristic superlattice reflections corresponding to
                      oxygen vacancies. Despite the occurrence of oxygen
                      vacancies, HERFD-XANES measurements on the Ce L3-edge
                      revealed that Ce incorporates as Ce4+ into the structures
                      but involves local distortion that resembles cluster
                      behavior and loss of nearest-neighbors. In comparison,
                      HERFD-XANES measurements on the Nd L3-edge supported by
                      electronic structure calculations reveal that Nd3+ adopts a
                      local coordination environment similar to the long-range
                      C-type structure while providing charge balancing for the
                      formation of oxygen defects. Th L3-edge EXAFS analysis
                      reveals shorter average Th–O distances in the title
                      compounds in comparison to pristine ThO2 in addition to
                      shorter Th–O and Th–Ce distances compared to Th–Th or
                      Ce–Ce in the corresponding F-type binary oxides (ThO2 and
                      CeO2). These distances are further found to decrease with
                      the increased Nd content of the structures despite
                      simultaneous observation of the overall lattice structure
                      progressively expanding. Linear combination calculations of
                      the M-O bond lengths are used to help explain these
                      observations, where the role of oxygen defects, via Nd3+
                      incorporation, induces local bond contraction and enhanced
                      Th cation valence, leading to the observed increased lattice
                      expansion with progressive Nd3+ incorporation. Overall, the
                      investigation points to the significance of dissimilar
                      cations exhibiting variable short-range chemical behavior
                      and how it can affect the long-range structural chemistry of
                      complex oxides.},
      cin          = {IFN-2},
      ddc          = {660},
      cid          = {I:(DE-Juel1)IFN-2-20101013},
      pnm          = {1411 - Nuclear Waste Disposal (POF4-141) / BMBF 02NUK060B -
                      Verbundprojekt AcE: Grundlegende Untersuchungen zur
                      Immobilisierung von Actiniden mittels Einbau in
                      endlagerrelevante Festphasen, Teilprojekt B (02NUK060B)},
      pid          = {G:(DE-HGF)POF4-1411 / G:(BMBF)02NUK060B},
      typ          = {PUB:(DE-HGF)16},
      pubmed       = {38947849},
      UT           = {WOS:001246074900001},
      doi          = {10.1021/acsomega.4c02200},
      url          = {https://juser.fz-juelich.de/record/1029087},
}