Solvent effect of alcohols at the L-edge of iron in solution:: X-ray absorption and multiplet calculations

被引：24

作者：

Bonhommeau, Sebastien ^{[1
]}

Ottosson, Niklas ^{[1
,2
]}

Pokapanich, Wandared ^{[2
]}

Svensson, Svante ^{[2
]}

Eberhardt, Wolfgang ^{[1
]}

Bjorneholm, Olle ^{[2
]}

Aziz, Emad F. ^{[1
]}

机构：

[1] BESSY, D-12489 Berlin, Germany

[2] Uppsala Univ, Dept Phys & Mat Sci, SE-75121 Uppsala, Sweden

来源：

JOURNAL OF PHYSICAL CHEMISTRY B | 2008年 / 112卷 / 40期

关键词：

D O I：

10.1021/jp8071266

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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 L-2,L-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.

引用

页码：12571 / 12574

页数：4

共 22 条

[11] Multiplet effects in X-ray spectroscopy [J].