Ab initio study of ultrafast photochemical reaction dynamics of phenol blue

Phenol blue (PB) is a primary skeletal structure part of indoaniline dyes and well-known as a solvatochromic dye. It has been recently observed by pump-probe (PP) transient absorption measurements that PB shows ultrafast ground state recovery within a few hundred femtoseconds after photoexcitation. In this work, the ultrafast photochemical reaction mechanism of PB has been investigated using direct ab initio (CASSCF) nonadiabatic molecular dynamics with the trajectory surface hopping (TSH) method. The swarm of trajectories starting from the S1 Franck-Condon (FC) point has mostly shown surface hops (nonadiabatic transitions) from the S1 state to the S0 state at 110-120 fs in the vicinity of an S1/S0 conical intersection and after decay to the S0 state bifurcated into two (Reverse and Forward) directions with almost the same branching ratio and reached the vicinity of the S0 minimum energy point at 200-300 fs, which is in good agreement with the fast time component of the ground state recovery in the PP measurements. After reaching the vicinity of the S0 minimum energy point, the trajectories showed a coherent vibration of bending motion between quinoneimine and aniline rings with a low frequency of 43 cm-1, which presumably corresponds to a coherently photoexcitation-induced vibrational mode with a low frequency recently observed by the PP measurements.