Can time-dependent double hybrid density functionals accurately predict electronic excitation energies of BODIPY compounds?

Accurate predictions of the electronic excited states of BODIPY based dye sensitizers using spin-component-scaled double-hybrid functionals: a TD-DFT benchmark study

“…In fact, these findings are consistent with that of our recent benchmark study on small BODIPY chromophores, in which the range separated functionals (RSH and RSDH) were also among the worst performing ones with MAE values around 0.5 to 0.6 eV. 70 …”

“…As a matter of fact, we have also obtained this remarkable performance of the two spin-component-scaled functionals in our recent study about another set of BODIPY model compounds which are smaller than the dye sensitizers studied in this work. 70 It is interesting to note however, that the MAE values obtained using the two DSD functionals for the much larger and extended charge transfer dye sensitizers investigated in this work are slightly better than the smaller set of BODIPY chromophores studied previously. 70 For instance, the MAE for DSD-BLYP functional is 0.083 eV for the larger dye sensitizers, and 0.119 eV for the significantly smaller size BODIPY set of chromophores.…”

“… 70 It is interesting to note however, that the MAE values obtained using the two DSD functionals for the much larger and extended charge transfer dye sensitizers investigated in this work are slightly better than the smaller set of BODIPY chromophores studied previously. 70 For instance, the MAE for DSD-BLYP functional is 0.083 eV for the larger dye sensitizers, and 0.119 eV for the significantly smaller size BODIPY set of chromophores. 70 Not only the DSD functionals are the most accurate functionals among the large set of other functionals tested in this work, but those two empirical DH functionals are comparable with the excellent performance of the more expensive wavefunction based coupled-cluster methods in the gas phase, such as the LCC2* (ref.…”

“…Indeed, the increase of calculated errors in the absorption energies obtained by the global hybrids as a function of the percentage of the HF exchange of BODIPY compounds is not surprising, as it was also revealed in our previous study for a set of smaller BODIPY chromophores. 70 …”

“…In a recent benchmark study, where we have tested the double hybrid functionals on a set of relatively small BODIPY chromophores, we found that the dispersion-corrected, spin-component-scaled, double-hybrid (DSD) functionals DSD-BLYP and DSD-PBEP86 perform very well, with MAE values close to 0.1 eV. 70 The average of errors found in that benchmark study using TD DH functionals fall in the range of errors of the more expensive coupled-cluster methods. 55,66 In this work, we have decided to extend the benchmark of double hybrid functionals, on larger dyes that are designed on push–pull architectures and having electronic transitions that are characterized with significant long range charge transfer.…”