INOR 738 |
| Electronic structure calculations were performed of [FeCl4]- in the ground and excited electronic states using different electronic structure methods. All density functional methods tested underestimated the ligand field transitions, but the three-parameter hybrid density functional methods (ex. B3LYP) were found to give ligand field transitions that are in best overall agreement with experimental results compared to other methods, including some post-HF methods like MP4, QCISD(T) and CCSD(T). Analysis of the DFT and post-Hartree-Fock results suggest an alternative interpretation and assignment of the observed ligand field spectra. In particular, the lowest energy ligand field transitions were found to be very sensitive to the D2d distortion angle. A single parameter hybrid DFT method based only on the amount of Hartree-Fock exchange was optimized for each correlation functional, to best reproduce the experimentally determined lowest energy ligand field transitions of [FeCl4]-. The optimized functionals were used to compute additional excited state transitions for [FeCl4]-, and the results are compared to experiment. |
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Theoretical and Computational Chemistry
7:00 PM-10:00 PM, Tuesday, August 21, 2007 BCEC -- Exhibit Hall - B2, Poster
Division of Inorganic Chemistry |