Fast and Accurate Electronic Excitations in Cyanines with the Many-Body Bethe-Salpeter Approach
Résumé
The accurate prediction of the optical signatures of cyanine derivatives remains an important challenge in theoretical chemistry. Indeed, up to now, only the most involved quantum chemical methods (CAS-PT2, CC, DMC, etc.) yield consistent and accurate data, impeding the applications on real-life molecules. Here, we investigate the lowest lying singlet excitation energies of increasingly long cyanine dyes within the GW and Bethe−Salpeter Green's function many-body perturbation theory. Our results are in remarkable agreement with available coupled-cluster 17 (exCC3) data, bringing these two single-reference perturbation techniques within a 18 0.05 eV maximum discrepancy. By comparison, available TD-DFT calculations with 19 various semilocal, global, or range-separated hybrid functionals, overshoot the 20 transition energies by a typical error of 0.3−0.6 eV. The obtained accuracy is achieved 21 with a parameter-free formalism that offers similar accuracy for metallic or insulating 22 finite size or extended systems.