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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 (Na 10 Cl 9 ) + , (NaCl) 10 , and (Na 9 Cl 10 ) - 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-H 2 O 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.

Condensation particle counter (CPC) instruments are commonly used to detect atmospheric nanoparticles. They operate on the basis of condensing an organic working fluid on the nanoparticle seeds to grow the particles to a detectable size, and at the size of few nanometers, their efficiency depends on how well the working fluid interacts with the seeds under the measurement conditions. This study models the first steps of heterogeneous nucleation of two working fluids commonly used in CPCs (diethylene glycol (DEG) and n -butanol) onto two positively charged seeds, ammonium bisulfate and tetramethylammonium bromide. The nucleation process is modeled on a molecular level using a combination of systematic configurational sampling and density functional theory (DFT). We take into account the conformational flexibility of DEG and n -butanol and determine the key factors that can improve the efficiency of nanoparticle measurements by CPCs. The results show that hydrogen bonding between the seed and the working fluid molecules is central to the adsorption of the first DEG/ n -butanol molecules onto the seeds. However, intermolecular hydrogen bonding between the adsorbed molecules can also enhance the nucleation process for the weakly adsorbing vapor molecules. Accordingly, the heterogeneous nucleation probability is higher for working fluid-nanoparticle combinations with a higher potential for hydrogen bonding; in this case, DEG and ammonium bisulfate. Moreover, conformational analysis and methodology evaluations indicate that the consideration of adsorbate conformers and step-wise addition of the vapor molecules to the seeds is not essential for qualitative modeling of heterogeneous nucleation systems, at least for systems where the adsorbate and seed chemical properties are clearly different. This is the first molecular-level modeling study reporting detailed chemical reasons for experimentally observed seed and working fluid preferences in CPCs and reproducing the experimental observations. Our presented approach can be likely used for predicting preferences in similar nucleating systems.

Although both atomic carbon and water are omnipresent in human life, there is a debate about the possibility of carbon reaction with water. Some low-temperature spectroscopic investigations have rejected the reaction, whereas some room-temperature experiments and theoretical studies have accepted the possibility of the reaction by reporting rate coefficients ranging from 10 5 to 10 9 L mol -1 s -1 . This study provides new lines of evidence about the reaction through exploration of the reaction mechanism using the CCSD(T) method and solving the corresponding master equation by following two main approaches. According to the results, the rate coefficient of the reaction is significantly influenced by the tunneling and hindered rotation effects, in addition to the selected total angular momentum ( J ). Furthermore, the total rate coefficient of the reaction increases dramatically (from 10 7 to 10 11 L mol -1 s -1 ) with the rise of temperature from 100 to 4000 K, while the total rate coefficient is insensitive to pressure (0.1-10 atm). Despite some differences between the results of the two approaches, the rate coefficients of both methods are consistent with the previously reported rate coefficients. Also, in agreement with the previous studies, the major products are 2 HOC + 2 H and 2 HCO + 2 H. In general, the findings approve the occurrence of the title reaction and indicate that the mentioned conflict is due to the sensitivity of the reaction to the investigated temperature and J level. The sensitivity does not permit low-temperature spectroscopic studies to detect any products and varies the measured and calculated rate coefficients.