Microhydration of 2‑Naphthol at Ground, First Excited Triplet, and First Excited Singlet States: A Case Study on Photo Acids

Molecular interactions of 2-naphthol (nap) with water molecules are studied at the ground, first excited triplet and first excited singlet states, applying DFT and TD-DFT methods. The minimum energy structure of hydrated clusters of 2-naphthol up to four water molecules are selected from several possible input geometries. It is observed that the minimum energy conformer of the tetra-hydrate of 2-naphthol has proton transfer occurring from nap to solvent water molecules, in its first excited singlet state. This is however not observed in case of its ground or first excited triplet state. It is consistent with the fact that the pK a of nap in the first excited singlet state is very much lower compared to the ground and first excited triplet state. This is also reflected in the O–H potential energy profile of tetrahydrate of nap, obtained by performing a rigid potential energy scan of the dissociating O–H bond of nap at ground, first excited triplet and first excited singlet states. Frequency of O–H stretching vibration of 2-napthol and its hydrated clusters in the ground (S0) as well as in the first excited singlet (S1) state are calculated and compared with the available experimental data. The performance of macroscopic solvation model is also examined in the ground and these excited states.