Distorted Tetrahedral CoIIin K5H[CoW12O40]·xH2O Probed by 2p3d Resonant Inelastic X-ray Scattering.
The Co 2p3/2X-ray absorption spectroscopy and high-energy-resolution (∼0.09 eV fwhm) 2p3d resonant inelastic X-ray scattering (RIXS) spectra of the single-cobalt-centered polyoxometalate K5H[CoW12O40]·xH2O were measured. The low-energy dd transition features at 0.55 eV, unmeasurable with ultraviolet-visible (UV/vis) spectroscopy, were experimentally revealed in 2p3d RIXS spectra. RIXS simulations based on ligand-field multiplet theory were performed to assess the potential cobalt tetragonal symmetry distortion, which is described with the ligand-field parameters 10Dq(-0.54 eV), Ds(-0.08 eV), and Dt(0.005 eV). Because 2p3d RIXS probes not only the optical spin-allowed transitions but also the spin-forbidden transitions, we show that the current 2p3d RIXS simulation enables a series of dd feature assignments with higher accuracy than those from previous optical data. Furthermore, by wave-function decomposition analyses, we demonstrate the more realistic and detailed origins of a few lowest dd transitions using both one-electron-orbital and term-symbol descriptions.
Inorganic Chemistry & Catalysis, Debye Institute for Nanomaterials Science, Utrecht University , Universiteitsweg 99, 3584 CG Utrecht, The Netherlands.
Boyang
B
Liu
Inorganic Chemistry & Catalysis, Debye Institute for Nanomaterials Science, Utrecht University , Universiteitsweg 99, 3584 CG Utrecht, The Netherlands.
Ru-Pan
RP
Wang
Department of Chemistry, Emory University , Atlanta, Georgia 30322, United States.
Elliot N
EN
Glass
Department of Chemistry, Emory University , Atlanta, Georgia 30322, United States.
Craig L
CL
Hill
Department of Chemistry, University of California-Berkeley , 419 Latimer Hall, Berkeley, California 94720, United States.
Tanja
T
Cuk
National Synchrotron Radiation Research Center (NSRRC) , Hsinchu 30076, Taiwan.
Jun
J
Okamoto
National Synchrotron Radiation Research Center (NSRRC) , Hsinchu 30076, Taiwan.
Di-Jing
DJ
Huang
Inorganic Chemistry & Catalysis, Debye Institute for Nanomaterials Science, Utrecht University , Universiteitsweg 99, 3584 CG Utrecht, The Netherlands.
Matti M
MM
van Schooneveld
Inorganic Chemistry & Catalysis, Debye Institute for Nanomaterials Science, Utrecht University , Universiteitsweg 99, 3584 CG Utrecht, The Netherlands.
Frank M F
FM
de Groot