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

In this paper, we investigate the role of electron correlation in predicting the S1-S0 and T1-S0 excitation energies and, hence, the singlet-triplet gap (ΔEST) in a set of cyclazines, which act as templates for potential candidates for fifth generation organic light emitting diode materials. This issue has recently garnered much interest with the focus being on the inversion of the ΔEST, although experiments have indicated near degenerate levels with both positive and negative being within the experimental error bar [J. Am. Chem. Soc. 102, 6068 (1980), J. Am. Chem. Soc. 108, 17(1986)]. We have carried out a systematic and exhaustive study of various excited state electronic structure methodologies and identified the strengths and shortcomings of the various approaches and approximations in view of this challenging case. We have found that near degeneracy can be achieved either with a proper balance of static and dynamic correlation in multireference theories or with state-specific orbital corrections, including its coupling with correlation. The role of spin contamination is also discussed. Eventually, this paper seeks to produce benchmark numbers for establishing cost-effective theories, which can then be used for screening derivatives of these templates with desirable optical and structural properties. Additionally, we would like to point out that the use of domain-based local pair natural orbital-similarity transformed EOM-coupled cluster singles and doubles as the benchmark for ΔEST [as used in J. Phys. Chem. A 126(8), 1378 (2022), Chem. Phys. Lett. 779, 138827 (2021)] is not a suitable benchmark for these classes of molecules.