Assessing the density functional theory-based multireference configuration interaction (DFT/MRCI) method for transition metal complexes
- Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr (Germany)
We report an assessment of the performance of density functional theory-based multireference configuration interaction (DFT/MRCI) calculations for a set of 3d- and 4d-transition metal (TM) complexes. The DFT/MRCI results are compared to published reference data from reliable high-level multi-configurational ab initio studies. The assessment covers the relative energies of different ground-state minima of the highly correlated CrF{sub 6} complex, the singlet and triplet electronically excited states of seven typical TM complexes (MnO{sub 4}{sup −}, Cr(CO){sub 6}, [Fe(CN){sub 6}]{sup 4−}, four larger Fe and Ru complexes), and the corresponding electronic spectra (vertical excitation energies and oscillator strengths). It includes comparisons with results from different flavors of time-dependent DFT (TD-DFT) calculations using pure, hybrid, and long-range corrected functionals. The DFT/MRCI method is found to be superior to the tested TD-DFT approaches and is thus recommended for exploring the excited-state properties of TM complexes.
- OSTI ID:
- 22254848
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 19 Vol. 140; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
Similar Records
Theoretical investigation of the energies and geometries of photoexcited uranyl(VI) ion: A comparison between wave-function theory and density functional theory