Competing Nonadiabatic Relaxation Pathways for Near-UV Excited ortho-Nitrophenol in Aqueous Solution

Nitrophenols are atmospheric pollutants found in brown carbon aerosols produced by biomass burning. Absorption of solar radiation by these nitrophenols contributes to atmospheric radiative forcing, but quantifying this climate impact requires better understanding of their photochemical pathways. Here, the photochemistry of near-UV (λ = 350 nm) excited ortho-nitrophenol in aqueous solution is investigated using transient absorption spectroscopy and time-resolved infrared spectroscopy over the fs to μs time scale to characterize the excited states, intermediates, and photoproducts. Interpretation of the transient spectroscopy data is supported by quantum chemical calculations using linear-response time-dependent density functional theory (LR-TDDFT). Our results indicate efficient nonradiative decay via an S₁(ππ*)/S₀ conical intersection leading to hot ground state ortho-nitrophenol which vibrationally cools in solution. A previously unreported minor pathway involves intersystem crossing near an S₁(nπ*) minimum, with decay of the resulting triplet ortho-nitrophenol facilitated by deprotonation. These efficient relaxation pathways account for the low quantum yields of photodegradation.