Predicting Gas-Particle Partitioning Coefficients of Atmospheric Molecules with Machine Learning

Abstract. The formation, properties and lifetime of secondary organic aerosols in the atmosphere are largely determined by gas-particle partitioning coefficients of the participating organic vapours. Since these coefficients are often difficult to measure and to compute, we developed a machine learning model to predict them given molecular structure as input. Our data-driven approach is based on the dataset by Wang et al. (Atmos. Chem. Phys., 17, 7529 (2017)), who computed the partitioning coefficients and saturation vapour pressures of 3414 atmospheric oxidation products from the master chemical mechanism using the COSMOtherm program. We trained a kernel ridge regression (KRR) machine learning model on the saturation vapour pressure (Psat), and on two equilibrium partitioning coefficients: between a water-insoluble organic matter phase and the gas phase (KWIOM/G), and between an infinitely dilute solution with pure water and the gas phase (KW/G). For the input representation of the atomic structure of each organic molecule to the machine, we tested different descriptors. We find that the many-body tensor representation (MBTR) works best for our application, but the topological fingerprint (TopFP) approach is almost as good, and is significantly more cost effective. Our best machine learning model (KRR with a Gaussian kernel + MBTR) predicts Psat and KWIOM/G to within 0.3 logarithmic units and KW/G to within 0.4 logarithmic units of the original COSMOtherm calculations. This is equal or better than the typical accuracy of COSMOtherm predictions compared to experimental data (where available). We then applied our machine learning model to a dataset of 35,383 molecules that we generated based on a carbon 10 backbone functionalized with 0 to 6 carboxyl, carbonyl or hydroxyl groups to evaluate its performance for polyfunctional compounds with potentially low Psat. The resulting saturation vapor pressure and partitioning coefficient distributions were physico-chemically reasonable, and the volatility predictions for the most highly oxidized compounds were in qualitative agreement with experimentally inferred volatilities of atmospheric oxidation products with similar elemental composition.