Search results for "ilmakemia"
showing 9 items of 9 documents
A study on the fragmentation of sulfuric acid and dimethylamine clusters inside an atmospheric pressure interface time-of-flight mass spectrometer
2022
Abstract. Sulfuric acid and dimethylamine vapours in the atmosphere can form molecular clusters, which participate in new particle formation events. In this work, we have produced, measured, and identified clusters of sulfuric acid and dimethylamine using an electrospray ionizer coupled with a planar-differential mobility analyser, connected to an atmospheric pressure interface time-of-flight mass spectrometer (ESI–DMA–APi-TOF MS). This set-up is suitable for evaluating the extent of fragmentation of the charged clusters inside the instrument. We evaluated the fragmentation of 11 negatively charged clusters both experimentally and using a statistical model based on quantum chemical data. Th…
A predictive model for salt nanoparticle formation using heterodimer stability calculations
2021
Acid–base clusters and stable salt formation are critical drivers of new particle formation events in the atmosphere. In this study, we explore salt heterodimer (a cluster of one acid and one base) stability as a function of gas-phase acidity, aqueous-phase acidity, heterodimer proton transference, vapor pressure, dipole moment and polarizability for salts comprised of sulfuric acid, methanesulfonic acid and nitric acid with nine bases. The best predictor of heterodimer stability was found to be gas-phase acidity. We then analyzed the relationship between heterodimer stability and J4×4, the theoretically predicted formation rate of a four-acid, four-base cluster, for sulfuric acid salts ove…
Supplementary data for the article "Predicting liquid-liquid phase separation in ternary organic-organic-water mixtures"
2023
Artikkelin "Predicting liquid-liquid phase separation in ternary organic-organic-water mixtures" lisäaineisto. The data set contains the supplementary data of the article "Predicting liquid-liquid phase separation in ternary organic-organic-water mixtures" published in Phys. Chem. Chem. Phys. The data includes cosmo-files used in the COSMOtherm calculations of the article.
Microscopic Insights Into the Formation of Methanesulfonic Acid–Methylamine–Ammonia Particles Under Acid-Rich Conditions
2022
Understanding the microscopic mechanisms of new particle formation under acid-rich conditions is of significance in atmospheric science. Using quantum chemistry calculations, we investigated the microscopic formation mechanism of methanesulfonic acid (MSA)–methylamine (MA)–ammonia (NH3) clusters. We focused on the binary (MSA)2n-(MA)n and ternary (MSA)3n-(MA)n-(NH3)n, (n = 1–4) systems which contain more acid than base molecules. We found that the lowest-energy isomers in each system possess considerable thermodynamic and dynamic stabilities. In studied cluster structures, all bases are protonated, and they form stable ion pairs with MSA, which contribute to the charge transfer and the stab…
Modeling atmospheric aging of small-scale wood combustion emissions: distinguishing causal effects from non-causal associations
2022
Small-scale wood combustion is a significant source of particulate emissions. Atmospheric transformation of wood combustion emissions is a complex process involving multiple compounds interacting simultaneously. Thus, an advanced methodology is needed to study the process in order to gain a deeper understanding of the emissions. In this study, we are introducing a methodology for simplifying this complex process by detecting dependencies of observed compounds based on a measured dataset. A statistical model was fitted to describe the evolution of combustion emissions with a system of differential equations derived from the measured data. The performance of the model was evaluated using simu…
Emissions of atmospherically reactive gases nitrous acid and nitric oxide from Arctic permafrost peatlands
2022
Soils are important sources of nitric oxide (NO) and nitrous acid (HONO) in the atmosphere. These nitrogen (N)-containing gases play a crucial role in atmospheric chemistry and climate at different scales because of reactions modulated by NO and hydroxyl radicals (OH), which are formed via HONO photolysis. Northern permafrost soils have so far remained unexplored for HONO and NO emissions despite their high N stocks, capacity to emit nitrous oxide (N2O), and enhancing mineral N turnover due to warming and permafrost thawing. Here, we report the first HONO and NO emissions from high-latitude soils based on measurements of permafrost-affected subarctic peatlands. We show large HONO (0.1–2.4 µ…
Experimental FTIR-MI and Theoretical Studies of Isocyanic Acid Aggregates
2023
Homoaggregates of isocyanic acid (HNCO) were studied using FTIR spectroscopy combined with a low-temperature matrix isolation technique and quantum chemical calculations. Computationally, the structures of the HNCO dimers and trimers were optimized at the MP2, B3LYPD3 and B2PLYPD3 levels of theory employing the 6-311++G(3df,3pd) basis set. Topological analysis of the electron density (AIM) was used to identify the type of non-covalent interactions in the studied aggregates. Five stable minima were located on the potential energy surface for (HNCO)2, and nine were located on the potential energy surface for (HNCO)3. The most stable dimer (D1) involves a weak, almost linear N-H⋯N hydrog…
Matrix Isolation FTIR and Theoretical Study of Weakly Bound Complexes of Isocyanic Acid with Nitrogen.
2021
Weak complexes of isocyanic acid (HNCO) with nitrogen were studied computationally employing MP2, B2PLYPD3 and B3LYPD3 methods and experimentally by FTIR matrix isolation technique. The results show that HNCO interacts specifically with N2. For the 1:1 stoichiometry, three stable minima were located on the potential energy surface. The most stable of them involves a weak, almost linear hydrogen bond from the NH group of the acid molecule to nitrogen molecule lone pair. Two other structures are bound by van der Waals interactions of N⋯N and C⋯N types. The 1:2 and 2:1 HNCO complexes with nitrogen were computationally tracked as well. Similar types of interactions as in the 1:1 complexes were …
Machine Learning for Predicting Chemical Potentials of Multifunctional Organic Compounds in Atmospherically Relevant Solutions
2022
We have trained the Extreme Minimum Learning Machine (EMLM) machine learning model to predict chemical potentials of individual conformers of multifunctional organic compounds containing carbon, hydrogen, and oxygen. The model is able to predict chemical potentials of molecules that are in the size range of the training data with a root-mean-square error (RMSE) of 0.5 kcal/mol. There is also a linear correlation between calculated and predicted chemical potentials of molecules that are larger than those included in the training set. Finding the lowest chemical potential conformers is useful in condensed phase thermodynamic property calculations, in order to reduce the number of computationa…