Comparative studies of the spectroscopy of CuCl2: DFT versus standard ab initio approaches.

The X²Πg-²Σg,X²Πg-²Δg, X²Πg-²Σu, X²Πg-²Πu transitions on CuCI2 have been studied using several exchange-correlation functionals from the various types of density functional theory (DET) approaches like local density approximation (LDA), generalized gradient approximation (GGA), hybrid and meta-GGA. The results are compared with the experience and with those coming from the most sophisticated nondynamic and dynamic electronic correlation treatments using the same relativistic effective core potentials and especially developed basis sets to study the electronic structure of the five lowest states and the corresponding vertical and adiabatic transition energies. The calculated transition energies for three of the hybrid functionals (B3LYP, B97-2, and PBE0) are in very good agreement with the benchmark ab initio results and experimental figures. All of the other functionals largely overestimate the X²Πg-²Σg and X²Πg-²Δgtransition energies, many of them even placing the ²Δg ligand field state above the charge transfer ²Πu and ²Σu+ states. The relative weight of the Hartree-Fock exchange in the definition of the functional used appears to play a key role in the accurate description of the ASΣ density defined by the orientation of the 3d hole (σ,π,or δ) on Cu in the field of both chlorine atoms, hut no simple connection of this weight with the quality of the spectra has been found. Mulliken charges and spin densities are carefully analyzed; a possible link between the extent of spin density on the metal for the X²Πg state and the performance of the various functionals was observed, suggesting that those that lead to the largest values (close to 0.65) are the ones that best reproduce these four transitions. Most functionals lead to a remarkably low ionicity for the three ligand field states even for the best performing functionals, compared to the complete active space (SCF) (21, 14) ab initio values. These findings show that not only large variational ab initio calculations Can produce reliable spectroscopic results for extremely complex systems where delicate electronic correlation effects have to he carefully dealt with. However, those functionals that were recently shown to perform best for a series of molecular properties. [ABSTRACT FROM AUTHOR]