Secondary organic aerosol formation by heterogeneous reactions of aldehydes and ketones: a quantum mechanical study

Experimental studies have provided convincing evidence that aerosol-phase heterogeneous chemical reactions (possibly acid-catalyzed) are involved to some extent in the formation of secondary organic aerosol (SOA). We present a stepwise procedure to determine physical properties such as heats of formation, standard entropies, Gibbs free energies of formation, and solvation energies from quantum mechanics (QM), for various short-chain aldehydes and ketones. We show that quantum mechanical gas-phase Gibbs free energies of formation compare reasonably well with the literature values with a root-mean-square (RMS) value of 1.83 kcal/mol for the selected compounds. These QM results are then used to determine the equilibrium constants (reported as log K) of aerosol-phase chemical reactions, including hydration reactions and aldol condensation for formaldehyde, acetaldehyde, acetone, butanal, hexanal, and glyoxal. Results are in qualitatively agreement with previous studies. In addition, the QM results for glyoxal reactions are consistent with experimental observations. To our knowledge, this is the first QM study that supports observations of atmospheric particle-phase reactions. Despite the significant uncertainties in the absolute values from the QM calculations, the results are potentially useful in determining the relative thermodynamic tendency for atmospheric aerosol-phase reactions.