Theoretical predictions of the spectroscopic properties of BODIPY dyes: Effects of the fused aromatic and heteroaromatic rings at the b, g bonds

Radiative lifetime of a BODIPY dye as calculated by TDDFT and EOM-CCSD methods: solvent and vibronic effects

“…In particular, an important effort has concerned the benchmarking of methods for the calculation of vertical and 0-0 transition energies (usually for the S 1 state) in different series of BODIPY-based compounds. 18,20,23,24,30,31,35,36 These studies have shown that time dependent density functional theory (TDDFT) calculations generally significantly overestimate the S 1 excitation energy by about 0.3-0.5 eV. Nevertheless, because of the rather systematic nature of this deviation, the TDDFT method usually performs well in predicting the shifts in energy induced by various substituents or by chemical modifications of the BODIPY core.…”

“…30 These correlation effects can in principle be accounted for by wavefunction-based methods such as the configuration interaction (CI), coupled-cluster (CC) and complete active space self-consistent field (CASSCF) methods. Therefore, several calculations were performed using correlated methods including double excitations 17,24,28,30,31,36 (CIS(D), SOS-CIS(D), CC2, LCC2*, EOM-CCSD, SAC-CI, etc) and describing the multiconfigurational character 14,27,30,32 (CASPT2, RASPT2). For example, a very accurate reproduction of 0-0 energies (mean absolute error below 0.1 eV) was obtained using SOS-CIS(D) for a series of BODIPY dyes, 24 provided that the solvent and vibronic effects (calculated with PCM/TDDFT) are included.…”