Ab initio QM/MM molecular dynamics study on the excited-state hydrogen transfer of 7-azaindole in water solution.

Ab initio molecular dynamics (AIMD) simulations for the excited-state hydrogen transfer (ESHT) reaction of 7-azaindole (7AI-(H2O)n; n = 1, 2) clusters in the gas phase and in water are presented. The effective fragment potential (EFP) is employed to model the surrounding water molecules. The AIMD simulations for 7AI-H2O and 7AI-(H2O)2 clusters show an asynchronous hydrogen transfer at t approximately 50 fs after the photoexcitation. While the ESHT mechanism for 7AI-H2O in water does not change appreciably compared with that in the gas phase, the AIMD simulations on 7AI-(H2O)2 in water solution exhibit two different mechanisms. Since the tautomer form is lower in energy compared to the normal form in the S1 state, 7AI and (H2O) n fragments separate from each other after the ESHT. With the use of the results of the AIMD trajectories, the minimum energy conical intersection point in the tautomer region has also been located.