TY - JOUR
T1 - An investigation of the unusual 57Fe Mössbauer quadrupole splittings and isomer shifts in 2 and 3-coordinate Fe(II) complexes
AU - Zhang, Yong
AU - Oldfield, Eric
PY - 2003/7/21
Y1 - 2003/7/21
N2 - The 57Fe Mössbauer quadrupole splittings (ΔEQ) and isomer shifts (δFe) in 3-coordinate high-spin Fe(II) complexes are unusually small, and previous attempts to reproduce their ΔEQ values have been unsuccessful. We show here that, by using large structural models and basis sets, both ΔEQ and δFe values can be quite accurately predicted by using density functional theory. Four systems were investigated: the three 3-coordinate species [LFeX]0 (L = β-diketiminate; X = Cl-, CH3-) and [Fe(SC6H2-2,4,6-tBu3)3]-, in addition to an uncommon 2-coordinate high-spin ferrous thiolate, [Fe(SC6H3-2,6-mes2)2] (mes = mesityl = 2,4,6-Me3C6H2). Both Gaussian-type-orbital and Slater-type-orbital basis sets were investigated, and both yielded ΔEQ and δFe values in good accord with experiment. There were no improvements in these property predictions when (approximate) relativistic effects were included in the calculations. An MO analysis provided a detailed picture of the origin of the small ΔEQ values seen in the 3-coordinate complexes. These results extend the scope of DFT/Mössbauer investigations beyond the 4-6-coordinate systems described previously to 2- and 3-coordinate systems, which should open the way to using these parameters in structure refinement, especially in large systems, such as proteins.
AB - The 57Fe Mössbauer quadrupole splittings (ΔEQ) and isomer shifts (δFe) in 3-coordinate high-spin Fe(II) complexes are unusually small, and previous attempts to reproduce their ΔEQ values have been unsuccessful. We show here that, by using large structural models and basis sets, both ΔEQ and δFe values can be quite accurately predicted by using density functional theory. Four systems were investigated: the three 3-coordinate species [LFeX]0 (L = β-diketiminate; X = Cl-, CH3-) and [Fe(SC6H2-2,4,6-tBu3)3]-, in addition to an uncommon 2-coordinate high-spin ferrous thiolate, [Fe(SC6H3-2,6-mes2)2] (mes = mesityl = 2,4,6-Me3C6H2). Both Gaussian-type-orbital and Slater-type-orbital basis sets were investigated, and both yielded ΔEQ and δFe values in good accord with experiment. There were no improvements in these property predictions when (approximate) relativistic effects were included in the calculations. An MO analysis provided a detailed picture of the origin of the small ΔEQ values seen in the 3-coordinate complexes. These results extend the scope of DFT/Mössbauer investigations beyond the 4-6-coordinate systems described previously to 2- and 3-coordinate systems, which should open the way to using these parameters in structure refinement, especially in large systems, such as proteins.
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U2 - 10.1021/jp030177q
DO - 10.1021/jp030177q
M3 - Article
AN - SCOPUS:0042705192
SN - 1520-6106
VL - 107
SP - 7180
EP - 7188
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 29
ER -