Heterogeneous Ion-Induced Nucleation of Water and Butanol Vapors Studied via Computational Quantum Chemistry beyond Prenucleation and Critical Cluster Sizes.

Water and butanol are used as working fluids in condensation particle counters, and condensation of a single vapor onto an ion can be used as a simple model system for the study of ion-induced nucleation in the atmosphere. Motivated by this, we examine heterogeneous nucleation of water (H2O) and n-butanol (BuOH) vapors onto three positively (Li+, Na+, K+) and three negatively charged (F-, Cl-, Br-) ions using classical nucleation theory and computational quantum chemistry methods. We study phenomena that cannot be captured by Kelvin-Thomson equation for small nucleation ion cores. Our quantum chemistry calculations reveal the molecular mechanism behind ion-induced nucleation for each studied system. Typically, ions become solvated from all sides after several vapor molecules condense onto the ion. However, we show that the clusters of water and large negatively charged ions (Cl- and Br-) thermodynamically prefer the ion being migrated to the cluster surface. Although our methods generally do not show clear sign-preference for ion-water nucleation, we identified positive sign-preference for ion-butanol nucleation caused by the possibility to form stabilizing hydrogen bonds between butanol molecules condensed onto a positively charged ion. These bonds cannot form when butanol condenses onto a negatively charged ion. Therefore, we show that ion charge, its sign, as well as vapor properties have effects on the prenucleation and critical cluster/droplet sizes and also on the molecular mechanism of ion-induced nucleation.

Heterogeneous Nucleation of Butanol on NaCl: A Computational Study of Temperature, Humidity, Seed Charge, and Seed Size Effects.

Using a combination of quantum chemistry and cluster size distribution dynamics, we study the heterogeneous nucleation of n-butanol and water onto sodium chloride (NaCl)10 seeds at different butanol saturation ratios and relative humidities. We also investigate how the heterogeneous nucleation of butanol is affected by the seed size through comparing (NaCl)5, (NaCl)10, and (NaCl)25 seeds and by seed electrical charge through comparing (Na10Cl9)+, (NaCl)10, and (Na9Cl10)- seeds. Butanol is a common working fluid for condensation particle counters used in atmospheric aerosol studies, and NaCl seeds are frequently used for calibration purposes and as model systems, for example, sea spray aerosol. In general, our simulations reproduce the experimentally observed trends for the NaCl-BuOH-H2O system, such as the increase of nucleation rate with relative humidity and with temperature (at constant supersaturation of butanol). Our results also provide molecular-level insights into the vapor-seed interactions driving the first steps of the heterogeneous nucleation process. The main purpose of this work is to show that theoretical studies can provide molecular understanding of initial steps of heterogeneous nucleation and that it is possible to find cost-effective yet accurate-enough combinations of methods for configurational sampling and energy evaluation to successfully model heterogeneous nucleation of multicomponent systems. In the future, we anticipate that such simulations can also be extended to chemically more complex seeds.