In this thesis, the results from molecular dynamics (MD) simulations of nanoaerosol clusters are discussed. The connecting link of these studies is the Köhler theory, which is the theory of condensational growth and activation of cloud droplets to form clouds. By investigating parameters such as the surface tension, state of mixture and morphology of nanoaerosol particles, conclusions can be drawn to improve the Köhler theory to include the effects of organic compounds previously unaccounted for. For the terrestrial environment, the simulations show that the natural surfactant cis-pinonic acid, an oxidation product evaporated from boreal trees, spontaneously accumulates at the surface of nanoaerosol clusters and thereby reduces the surface tension. The surface tension depression is related to the concentration of the surfactant and the size of the clusters. Surface tension is an important parameter of the Köhler theory. A decrease of the surface tension can lower the critical water vapour supersaturation needed for cloud droplet activation, giving rise to more, but smaller cloud droplets (Twomey effect) which in turn could change the optical properties of the cloud. It was also shown that the three organic surfactants, being model compounds for so called Humic-like substances (HULIS) have the ability to form aggregates inside the nanoaerosol clusters. These HULIS aggregates can also promote the solubilization of hydrophobic organic carbon in the form of fluoranthene, enabling soot taking part in cloud drop formation. Dissolved intermediately surface-active free amino acids were shown to be of some relevance for cloud formation over remote marine areas. The MD simulations showed differences between the interacting forces for spherical and planar interfaces of amino acids solutions. This thesis has emphasized the surface-active properties of organic compounds, including model HULIS and amino acids and their effect on surface tension and molecular orientation including aggregate formation in nanoaerosol clusters and their activation to form droplets. This thesis shows that the Köhler equation does not fully satisfactory describe the condensational growth of nano-sized droplets containing organic surfactants. Different approaches are suggested as revisions of the Köhler theory. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Submitted. Paper 5: Manuscript.</p>

It is well known that atmospheric aerosols provide the sites for forming cloud droplets, and can affect the Earth's radiation budget through their interactions with clouds. The ability of aerosols to act as cloud condensation nuclei is a strong function of their chemical composition and size. The compositional complexity of aerosol prohibits their explicit treatment in atmospheric models of aerosol-cloud interactions. Nevertheless, the cumulative impact of organics on CCN activity is still required, as carbonaceous material can constitute up to 90% of the total aerosol, 10-70% of which is water soluble. Therefore it is necessary to characterize the water soluble organic carbon fraction by CCN activation, droplet growth kinetics, and surface tension measurements. In this thesis, we investigate the water soluble properties, such as surface tension, solubility, and molecular weight, of laboratory and ambient aerosols and their effect on CCN formation. A mechanism called Curvature Enhanced Solubility is proposed and shown to explain the apparent increased solubility of organics. A new method, called Köhler Theory Analysis, which is completely new, fast, and uses minimal amount of sample was developed to infer the molar volume (or molar mass) of organics. Due to the success of the technique in predicting the molar volume of laboratory samples, it was applied to aerosols collected in Mexico City. Additionally the surface tension, CCN activity, and droplet growth kinetics of these urban polluted aerosols were investigated. Studies performed for the water soluble components showed that the aerosols in Mexico City have surfactants present, can readily become CCN, and have growth similar to ammonium sulfate. Finally, aerosols from three different polluted sources, urban, bovine, and ship emissions, were collected and characterized. The data assembled was used to predict CCN concentrations and access our understanding of the system. From these analyses, it was evident that knowledge of the chemical composition and mixing state of the aerosol is necessary to achieve agreement between observations and predictions. The data obtained in this thesis can be introduced and used as constraints in aerosol-cloud interaction parameterizations developed for global climate models, which could lead to improvements in the indirect effect of aerosols.