TY - JOUR
T1 - Solvent effect of alcohols at the L-edge of iron in solution
T2 - X-ray absorption and multiplet calculations
AU - Bonhommeau, Sébastien
AU - Ottosson, Niklas
AU - Pokapanich, Wandared
AU - Svensson, Svante
AU - Eberhardt, Wolfgang
AU - Björneholm, Olle
AU - Aziz, Emad F.
PY - 2008/10/9
Y1 - 2008/10/9
N2 - The local electronic structure of Fe(III) and Fe(II) ions in different alcohol solutions (methanol, ethanol, propan-1-ol) is investigated by means of soft X-ray absorption spectroscopy at the iron L2,3-edge. The experimental spectra are compared with ligand field multiplet simulations. The solvated Fe(III) complex is found to exhibit octahedral symmetry, while a tetragonal symmetry is observed for Fe(II). A decrease in the solvent polarity increases the charge transfer from the oxygen of the alcohol to the iron ions. This conclusion is supported by Hartree-Fock calculations of the Mulliken charge distribution on the alcohols. A larger charge transfer is further observed from the solvent to Fe(III) compared to Fe(II), which is connected to the higher positive charge state of the former. Finally, iron ions in solution are found to prefer the high-spin configuration irrespective of their oxidation state.
AB - The local electronic structure of Fe(III) and Fe(II) ions in different alcohol solutions (methanol, ethanol, propan-1-ol) is investigated by means of soft X-ray absorption spectroscopy at the iron L2,3-edge. The experimental spectra are compared with ligand field multiplet simulations. The solvated Fe(III) complex is found to exhibit octahedral symmetry, while a tetragonal symmetry is observed for Fe(II). A decrease in the solvent polarity increases the charge transfer from the oxygen of the alcohol to the iron ions. This conclusion is supported by Hartree-Fock calculations of the Mulliken charge distribution on the alcohols. A larger charge transfer is further observed from the solvent to Fe(III) compared to Fe(II), which is connected to the higher positive charge state of the former. Finally, iron ions in solution are found to prefer the high-spin configuration irrespective of their oxidation state.
UR - http://www.scopus.com/inward/record.url?scp=54549088745&partnerID=8YFLogxK
U2 - 10.1021/jp8071266
DO - 10.1021/jp8071266
M3 - Article
AN - SCOPUS:54549088745
SN - 1520-6106
VL - 112
SP - 12571
EP - 12574
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 40
ER -