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

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.

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.