Benchmark of Bethe-Salpeter for Triplet Excited-States

摘要

We have evaluated the accuracy of the Bethe-Salpeter singlet triplet transition energies as well as singlet triplet and triplet triplet splittings for 20 organic molecules, using as reference the CC3 values determined by Thiel and co-workers with both the TZVP and aug-cc-pVTZ atomic basis sets. Our excitation energies are obtained on the basis of GW quasiparticle energy levels that are self-consistently converged with respect to the starting DFT eigenvalues. In its current form, BSE/GW is often unable to provide a balanced description of both singlet and triplet excited-states. While the singlet singlet and triplet triplet energy separations are obtained accurately, triplets are located too close in energy from the ground-state, by typically -0.55 eV when using standard functionals to generate the starting eigenstates. Applying the Tamm-Dancoff approximation upshifts the BSE triplet energies and allows reducing this error to ca. -0.40 eV, while using M06-HF eigenstates allows a further increase and hence a reduction of the error for triplet states, but at the cost of larger errors for the singlet excited-states. At this stage, the most accurate TD-DFT estimates therefore remain competitive for computing singlet triplet transition energies. Indeed, with M06-2X, irrespective of the application or not of the Tamm-Dancoff approximation and of the selected atomic basis set, the deviations obtained with TD-DFT are rather small.