Data for Determination of secondary species in solution through pump-selective transient absorption spectroscopy and explicit-solvent TDDFT

The measured electronic excitations of a given species in solution are often a composite of the electronic excitations of various equilibrium species of that molecule. It is common for a proportion of a species to deprotonate in solution, or form a tautomeric equilibrium, producing new peaks corresponding to the electronic excitations of the new species. One prominent example is alizarin in methanol, which at different temperatures, and in solutions with differing pH, has an isosbestic point between the two dominant excitations at 435 and 540 nm. The peak at 435 nm has been attributed to alizarin; the peak at 540 nm, however, more likely results from a species in equilibrium with alizarin. In this work, we were able to use both experimental and computational techniques to selectively examine electronic properties of both alizarin and its secondary species in equilibrium. This was achieved through use of transient electronic absorption spectroscopy, following selective photoexcitation of a specific species in equilibrium. The resulting transient electronic absorption spectra were compared to the known transient absorption spectra of potential secondary equilibrium species. The ground state absorption spectra associated with each species in equilibrium were predicted using linear-scaling time-dependent density functional theory with an explicitly modeled solvent and compared to the experimental result. This evidence from both techniques combines to suggest that the excitation at 540 nm arises from a specific monoanionic form of alizarin