Molecular Specificity and Proton Transfer Mechanisms in Aerosol Prenucleation Clusters Relevant to New Particle Formation

Atmospheric aerosol particles influence the Earth's radiative energy balance and cloud properties, thus impacting the air quality, human health, and Earth's climate change. Because of the important scientific and overarching practical implications of aerosols, the past two decades have seen extensive research efforts, with emphasis on the chemical compositions and underlying mechanisms of aerosol formation. It has been recognized that new particle formation (NPF) contributes up to 50% of atmospheric aerosols. Nowadays, the general consensus is that NPF proceeds via two distinct stages: the nucleation from gaseous precursors to form critical nuclei of sub-1-2 nm size, and the subsequent growth into large particles. However, a fundamental understanding of both the NPF process and molecular-level characterization of the critical size aerosol clusters is still largely missing, hampering the efforts in developing reliable and predictive aerosol nucleation and climate models.Both field measurements and laboratory experiments have gathered convincing evidence about the importance of volatile organic compounds (VOCs) in enhancing the nucleation and growth of aerosol particles. Numerous and abundant small clusters composed of sulfuric acid or bisulfate ion and organic molecules have been shown to exist in ∼2 nm sized aerosol particles. In particular, kinetic studies indicated the formation of clusters with one H2SO4 and one or two organics being the rate-limiting step.This Account discusses our effort in developing an integrated approach, which involves the laboratory cluster synthesis via electrospray ionization, size and composition analysis via mass spectrometry, photoelectron spectroscopic characterization, and quantum mechanics based theoretical modeling, to investigate the structures, energetics, and thermodynamics of the aerosol prenucleation clusters relevant to NPF. We have been focusing on the clusters formed between H2SO4 or HSO4- and the organics from oxidation of both biogenic and anthropogenic emissions. We illustrated the significant thermodynamic advantage by involving organic acids in the formation and growth of aerosol clusters. We revealed that the functional groups in the organics play critical roles in promoting NPF process. The enhanced roles were quantified explicitly for specific functional groups, establishing a Molecular Scale that ranks highly hierarchic intermolecular interactions critical to aerosol formation. The different cluster formation pathways, probably mimicking the various polluted industrial environments, that involve cis-pinonic and cis-pinic acids were unveiled as well. Furthermore, one intriguing fundamental phenomenon on the unusual protonation pattern, which violates the gas-phase acidity (proton affinity) prediction, was discovered to be common in sulfuric acid-organic clusters. The mechanism underlying the phenomenon has been rationalized by employing the temperature-dependent experiments of sulfuric acid-formate/halide model clusters, which could explain the high stability of the sulfuric acid containing aerosol clusters. Our work provides critical molecular-level information to shed light on the initial steps of nucleation of common atmospheric precursors and benchmarks critical data for large-scale theoretical modeling to further address problems of environmental interest.