Time-dependent density functional theory applied to ligand-field excitations and their circular dichroism in some transition metal complexes |
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| Authors: | Mark Rudolph Tom Ziegler Jochen Autschbach |
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| Affiliation: | 1. Department of Chemistry, State University of New York at Buffalo, Buffalo, NY 14260-3000, United States;2. Department of Chemistry, University of Calgary, Calgary, AB, Canada T1N-1N4;1. Fritz Haber Research Center, Institute of Chemistry, Hebrew University of Jerusalem, Jerusalem;2. Dept. of Materials and Interfaces, Weizmann Institute of Science, Rehovot, 76100, Israel;3. Theoretical Physics IV, University of Bayreuth, Bayreuth, D-95440, Germany |
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| Abstract: | Ligand-field transitions in [Co(en)3]3+ and [Rh(en)3]3+ as well as the low-energy part of the electronic spectrum of [Fe(phen)3]2+ are investigated with time-dependent density functional theory (TDDFT). There is a strong functional dependence for [Co(en)3]3+ and [Fe(phen)3]2+. ΔSCF methods reproduce the ligand-field singlet excitation energies of [Co(en)3]3+ and [Rh(en)3]3+ very well. The case of [Co(en)3]3+ is analyzed in some detail, in particular regarding the possibility of applying a charge-transfer (CT) correction [M.E. Casida, F. Gutierrez, J. Guan, F.-X. Gadea, D.R. Salahub, J.-P. Daudey, J. Chem. Phys. 113 (2000) 7062]. A simple CT correction would not be sufficient, but the magnitude of the charge transfer correction term in comparison with the calculated excitation energy appears to be indicative of self-interaction problems in the ground state electronic structure and in the calculated excitation energies. For the ligand-field transition of [Co(en)3]3+ a hybrid functional with about 25% exact exchange performs well. Range separation/long range correction/Coulomb attenuation offers little improvement for the ligand-field transitions in [Co(en)3]3+ because the occupied and unoccupied orbitals involved are in close spatial proximity. |
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