Methodological keys for accurate simulations

Abstract

Photoacids have a stronger propensity to give protons in their excited state than in their ground state which is a key feature for developing new material properties. Experimentally the determination of the excited state dissociation constants remains challenging as the lifetime of the photoacid, in its excited state, is too small. The present article establishes several protocols using the latest developments of the PCM-TD-DFT formalism e.g. both the corrected linear response (cLR) and state specific (SS) approaches. Equilibrium (eq) and non-equilibrium (neq) limits of the implicit solvent have been compared and we highlight that the SS-TD-DFT formalism provides figures in good agreement with experimental data once the eq limit is combined with the Born–Haber cycle or when the neq is used with the Föster cycle using absorption rather than emission transition energies.