Assessment of the ωB97 family for excited-state calculations

摘要

We benchmark three recently proposed range-separated hybrids, namely ωB97, ωB97X and ωB97XD in the framework of time-dependent density functional theory simulations of electronic absorption spectra. Comparisons are made with both theoretical estimates obtained by highly correlated approaches and experimental wavelengths of maximal absorption measured for important classes of $pi rightarrow pi^ast$ and $n rightarrow pi^ast$ chromogens. The amplitude of the errors induced by the lack of vibronic coupling in our computational model is also evaluated for five dyes. The performances of the ωB97 group are systematically compared to the results of other global and range-separated hybrids. It turns out that ωB97XD provides, in general, more accurate estimates than ωB97X and ωB97.