The vertical excitation energies and a lifetime of the two lowest singlet excited states of the conjugated polyenes from C2 to C22: Ab initio, DFT, and semiclassical MNDO-MD simulations.

Electronic excited states in the series of polyene molecules were explored. Optimal ground-state geometry was used for the evaluation of vertical excitation energies. Results of a chosen set of functionals were compared to post-HF methods (EOM-CCSD, NEVPT2, CASPT2, and MRCI). In addition, the semiempirical OM2/MNDO method using MRCISD computational level was confronted with the above-mentioned techniques. Despite the fact that the first excited state has a significant double-excitation character some functionals were able to qualitatively determine the correct state order (where the lowest excited state has a A g - $$ {\mathrm{A}}_{\mathrm{g}}^{-} $$ character). The most successful functionals in transition energies predictions were PBE, TPSS and BLYP in Tamm-Dancoff approach (TDA), which had the smallest root-mean-square deviation (RMSD) scoring towards the experimental values. Regarding RMSD scoring, the OM2/MNDO method performed fairly well, too. Besides absorption spectra, lifetimes of the first two excited states were estimated based on a stochastic approach exploring a swarm of OM2/MNDO hopping dynamics using the Tully fewest switch algorithm for each molecule. The longest lifetime of the first excited state (S 1 ) was found for decapentaene (about 5 ps). Further elongation of the conjugated chain caused a mild decrease of this value to ca 1.5 ps for docosaundecaene.