Benchmark computations of nearly degenerate singlet and triplet states of N-heterocyclic chromophores. II. Density-based methods

Abstract

In this paper, we demonstrate the performance of several density-based methods in predicting the inversion of S1 and T1 states of a few N-heterocyclic triangulene based fused ring molecules (popularly known as INVEST molecules) with an eye to identify a well performing but cost-effective preliminary screening method. Both conventional linear-response time-dependent density functional theory (LR-TDDFT) and ΔSCF methods (namely maximum overlap method, square-gradient minimization method, and restricted open-shell Kohn–Sham) are considered for excited state computations using exchange–correlation (XC) functionals from different rungs of Jacob’s ladder. A well-justified systematism is observed in the performance of the functionals when compared against fully internally contracted multireference configuration interaction singles and doubles and/or equation of motion coupled-cluster singles and doubles (EOM-CCSD), with the most important feature being the capture of spin-polarization in the presence of correlation. A set of functionals with the least mean absolute error is proposed for both the approaches, LR-TDDFT and ΔSCF, which can be more cost-effective alternatives for computations on synthesizable larger derivatives of the templates studied here. We have based our findings on extensive studies of three cyclazine-based molecular templates, with additional studies on a set of six related templates. Previous benchmark studies for subsets of the functionals were conducted against the domain-based local pair natural orbital-similarity transformed EOM-CCSD (STEOM-CCSD), which resulted in an inadequate evaluation due to deficiencies in the benchmark theory. The role of exact-exchange, spin-contamination, and spin-polarization in the context of DFT comes to the forefront in our studies and supports the numerical evaluation of XC functionals for these applications. Suitable connections are drawn to two and three state exciton models, which identify the minimal physics governing the interactions in these molecules.