Quantum mechanics/molecular mechanics studies on the mechanistic photophysics of sunscreen oxybenzone in methanol...

Herein, we have employed the QM(CASPT2//CASSCF)/MM method to explore the photophysical and photochemical mechanism of oxybenzone (OB) in methanol solution. Based on the optimized minima, conical intersections and crossing points, and minimum-energy reaction paths related to excited-state intramolecular proton transfer (ESIPT) and excited-state decay paths in the ¹ππ*, ¹nπ*, ³ππ*, ³nπ*, and S₀ states, we have identified several feasible excited-state relaxation pathways for the initially populated S₂(¹ππ*) state to decay to the initial enol isomer' S₀ state. The major one is the singlet-mediated and stretch-torsion coupled ESIPT pathway, in which the system first undergoes an essentially barrierless ¹ππ* ESIPT process to generate the ¹ππ* keto species, and finally realizes its ground state recovery through the subsequent carbonyl stretch-torsion facilitating S₁ → S₀ internal conversion (IC) and the reverse ground-state intramolecular proton transfer (GSIPT) process. The minor ones are related to intersystem crossing (ISC) processes. At the S₂(¹ππ*) minimum, an S₂(¹ππ*)/S₁(¹nπ*)/T₂(³nπ*) three-state intersection region helps the S₂ system branch into the T₁ state through a S₂ → S₁ → T₁ or S₂ → T₂ → T₁ process. Once it has reached the T₁ state, the system may relax to the S₀ state via direct ISC or via subsequent nearly barrierless ³ππ* ESIPT to yield the T₁ keto tautomer and ISC. The resultant S₀ keto species significantly undergoes reverse GSIPT and only a small fraction yields the trans-keto form that relaxes back more slowly. However, due to small spin-orbit couplings at T₁/S₀ crossing points, the ISC to S₀ state occurs very slowly. The present work rationalizes not only the ultrafast excited-state decay dynamics of OB but also its phosphorescence emission at low temperature.