Theoretical prediction of valence and Rydberg excited states: Minnesota exchange‐correlation functionals vs symmetry adapted cluster‐configuration interaction

Abstract

During this contribution, we present a benchmark investigation on the applicability of several Minnesota functionals from various classes like local meta‐generalized and meta‐nonseparable gradient approximations, hybrids, and range‐separated hybrids for describing the valence and Rydberg excitation energies of some organic compounds from different categories. Furthermore, the performances of Minnesota density functionals from density functional theory are also assessed against a wave function theory based approach in the context of excite states calculations, symmetry adapted cluster‐configuration interaction (SAC‐CI) method. Pragmatically, the singles and doubles linked excitation operators are considered in the SAC‐CI wave functions. With more or less different accountabilities of the considered methods, it is shown that the M06‐2X, M05‐2X, and M11 functionals have the best performances for valence excited states. On the other hand, for Rydberg excited states although the SAC‐CI method outperforms others, the statistical analyses reveal that the efficiency of some Minnesota functionals is also respectable.

Beyond Explored Functionals: A Computational Journey of Two-Photon Absorption

“…These functionals excel, outperforming their counterparts, due to their HF E x percentage and relatively reliable predictions of charge transfer. [111][112][113] A clear illustration of this independence from HF E x is observed in the comparison between M06-L and M06, where the former, with 0% E x , somewhat outperforms the latter, which has a 27% E x . This aspect sets the Minnesota functionals apart from others in terms of performance efficiency.…”

Beyond Explored Functionals: A Computational Journey of Two-Photon Absorption

“…However, an exception is observed in the case of Minnesota functionals. These functionals excel, outperforming their counterparts, due to their HF E x percentage and relatively reliable predictions of charge transfer. − A clear illustration of this independence from HF E x is observed in the comparison between M06-L and M06, where the former, with 0% E x , somewhat outperforms the latter, which has 27% E x . This aspect sets the Minnesota functionals apart from others in terms of performance efficiency.…”