10.1021/ic034716h.s001
Yannick Carissan
Yannick
Carissan
Jean-Louis Heully
Jean-Louis
Heully
Fabienne Alary
Fabienne
Alary
Jean-Pierre Daudey
Jean-Pierre
Daudey
Calculation of the Ground and Excited States of a Mixed Valence
Compound [Fe<sub>2</sub>(OH)<sub>3</sub>(NH<sub>3</sub>)<sub>6</sub>]<sup>2+</sup>: A Class II or Class III Compound?
American Chemical Society
2004
calculation
Hamiltonian
Fe 2
II
compound
approach
NH 3
OH
III
NH 3 EGP
2004-02-23 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/Calculation_of_the_Ground_and_Excited_States_of_a_Mixed_Valence_Compound_Fe_sub_2_sub_OH_sub_3_sub_NH_sub_3_sub_sub_6_sub_sup_2_sup_A_Class_II_or_Class_III_Compound_/3349069
The effective group potentials (EGP) approach has been successfully used for the computation of the ground and
excited states energies of the mixed valence compound [Fe<sub>2</sub>(OH)<sub>3</sub>(NH<sub>3</sub>)<sub>6</sub>]<sup>2+</sup>. It is the first time that for a system as
big as the complex presented above the ground and excited states are computed with their own orbitals and
studied in such a detailed way. First of all, the NH<sub>3</sub> EGP was validated by comparing calculations where NH<sub>3</sub> was
treated explicitly at different levels of calculations. Once the validation was obtained, the complete spectrum of the
compound under interest was calculated and compared with results obtained in a previous work by Barone et al.
and the spin Hamiltonian of widespread use. Some deviations from these predictive approaches were observed.
This allowed us to emphasize the importance of the dynamic correlation which is not included explicitly in the spin
Hamiltonian. Then, the influence of vibration has been studied by computing the potential energy curves obtained
when moving the (OH)<sub>3</sub> plane. This study shows that our calculations lead to a delocalized compound (class III)
as expected according to former experimental data.