Computer-generated atomistic microstructures of atmospheric nanoparticles are geometrically analyzed using Delaunay tessellation followed by Monte Carlo integration to compute their free and accessible volume. The nanoparticles studied consist of cis-pinonic acid (a biogenic organic aerosol component), inorganic ions (sulfate and ammonium), and water. Results are presented for the free or unoccupied volume in different domains of the nanoparticles and its dependence on relative humidity and organic content. We also compute the accessible volume to small penetrants such as water molecules. Most of the free volume or volume accessible to a penetrant as large as a water molecule is located in the domains occupied by organics. In contrast, regions dominated by inorganics do not have any cavities with sizes larger than 1 Å. Solid inorganic domains inside the particle are practically impermeable to any small molecule, thereby offering practically infinite resistance to diffusion. A guest molecule can find diffusive channels to wander around within the nanoparticle only through the aqueous and organic-rich domains. The largest pores are observed in nanoparticles with high levels of organic mass and low relative humidity. At high relative humidity, the presence of more water molecules reduces the empty space in the inner domains of the nanoparticle, since areas rich in organic molecules (which are the only ones where appreciable pores are found) are pushed to the outer area of the particle. This, however, should not be expected to affect the diffusive process as transport through the aqueous phase inside the particle will be, by default, fast due to its fluid-like nature.
© 2023 The Authors. Published by American Chemical Society.