Absorption Intensities of Organic Molecules from Electronic Structure Calculations versus Experiments: the Effect of Solvation, Method, Basis Set, and Transition Moment Gauge

Recently, we derived experimental oscillator strengths (OSs) from well-defined UV-visible absorption spectral peaks of 100 molecules in solution. Here, we focus on a subset of transitions with the highest reliability to further benchmark the OSs from several wave function methods and density functionals. We consider multiple basis sets, transition moment gauges (length, velocity, and mixed), and solvent corrections. Most transitions in the comparison set come from conjugated molecules and have π → π* character. We use an automated algorithm to assign computed transitions to experimental bands. OSs computed using the Tamm-Dancoff approximation (TDA), CIS, or EOM-CCSD exhibited a strong gauge dependence, which is diminished in linear response theories (TD-DFT, TD-HF, and to a smaller degree LR-CCSD). OSs calculated from TD-DFT with PCM solvent models are systematically larger than apparent OSs derived from experimental spectra. For example,