Wavelength-dependent intersystem crossing dynamics of phenolic carbonyls in wildfire emissions

Quantum chemical calculations were employed to construct Jablonski diagrams for a series of phenolic carbonyls, including vanillin, iso-vanillin, 4-hydroxybenzaldehyde, syringaldehyde, and coniferyl aldehyde. These molecules can enter the Earth's atmosphere from forest fire emissions and participate in photochemical reactions within the atmospheric condensed phase, including cloud and fog droplets and aqueous aerosol particles. This photochemistry alters the composition of light-absorbing organic content, or brown carbon, in droplets and particles through the formation and destruction of key chromophores. This study demonstrates that following photon absorption, phenolic carbonyls efficiently transition to triplet states <i>via</i> intersystem crossings (ISC), with rate coefficients ranging from 10⁹ to 10¹⁰ s^-1. Despite the presence of multiple potential ISC pathways due to several lower-lying triplet states, a single channel is found to dominate for each system. We further investigated the dependence of the ISC rate constant (<i>k</i>_ISC) on the vibrational excitation energy of the first accessible (ππ*) singlet excited state (S₁ or S₂, depending on the molecule), and compared it with the measured wavelength dependence of the photochemical quantum yield (<i>Φ</i>_loss). Although our model only accounts for intramolecular nonradiative electronic transitions, it successfully captures the overall trends. All studied molecules, except coniferyl aldehyde, exhibit saturation in the dependence of both <i>k</i>_ISC and <i>Φ</i>_loss on the wavelength (or vibrational excitation energy). In contrast, coniferyl aldehyde displays a single maximum, followed by a monotonic decrease as the excitation energy increases (wavelength decreases). This distinct behavior in coniferyl aldehyde may be attributed to the presence of a double-bonded substituent, which enhances π-electron conjugation, and reduces the exchange energy and thus the adiabatic energy gap between the S₁(ππ*) state and the target triplet state. For small energy gaps, the classical acceptor modes of the ISC process are less effective, leading to a low effective density of final states. Larger gaps enhance the effective density of states, making the wavelength dependence of the ISC more pronounced. Our calculations show that while all the studied phenolic carbonyls have similar acceptor modes, coniferyl aldehyde has a substantially smaller adiabatic gap (1700 cm^-1) than the other molecules. The magnitude of the adiabatic energy gap is identified as the primary factor determining the energy/wavelength dependence of the ISC rate and thus <i>Φ</i>_loss.