Microhydration effects on the electronic properties of protonated phenol: a theoretical study

The CC2 (second-order approximate coupled cluster method) has been employed to investigate microhydration effect on electronic properties of protonated phenol (PhH(+)) According to the CC2 calculation results on electronic excited states of microhydrated PhH(+), for the S1 and S2 electronic states, which are of (1)ππ* nature and belong to the A' representation of molecular Cs point group, a significant blue shift effect on the S1 and S2 electronic states, which are of 1ππ* nature and belong to the A' representation of molecular Cs point group, in comparison to corresponding transitions on bare cation (PhH(+)), has been predicted. Nevertheless, for the S3-S0 (1A'', 1σπ*) transition, a large red shift effect has been predicted. Furthermore, it has been found that the lowest (1)σπ* state plays a prominent role in the photochemistry of these systems. In the bare protonated phenol, the (1)σπ* state is a bound state with a broad potential curve along the OH stretching coordinate, while it is dissociative in microhydrated species. This indicates to a predissociation of the S1((1)ππ*) state by a low-lying (1)σπ* state, which leads the excited system to a concerted proton-transfer reaction from protonated chromophore to the solvent. The dissociative (1)σπ* state in monohydrated PhH(+) has small barrier, while increasing the solvent molecules up to three removes the barrier and consequently expedites the proton-transfer reaction dynamics.