Molecular properties affecting the hydration of acid–base clusters

Myllys, Nanna; Myers, Deanna C.; Smith, James N.

doi:10.1039/d1cp01704g

Cited by 13 publications

(15 citation statements)

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“…In particular, particle formation by nucleation is still not well understood and is difficult to represent in models (Kerminen et al, 2018). One of the dominant nucleation pathways is through salt formation, where the formation of a cluster is stabilized by the interactions between acid and base molecules, which enhances particle formation (Ball et al, 1999;Kirkby et al, 2011;Kürten et al, 2016;Nadykto and Yu, 2007;Nadykto et al, 2015;Wang et al, 2018). This nucleation pathway is particularly dominant in urban environments, where anthropogenic sources for acidic and basic gases are abundant (Ge et al, 2011;Kirkby et al, 2011;Qiu and Zhang, 2013;Weber et al, 1996;Wang et al, 2020).…”

Section: Introductionmentioning

confidence: 99%

A predictive model for salt nanoparticle formation using heterodimer stability calculations

2021

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Abstract. 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 over a range of monomer concentrations from 105 to 109 molec cm−3 and temperatures from 248 to 348 K and found that heterodimer stability forms a lognormal relationship with J4×4. However, temperature and concentration effects made it difficult to form a predictive expression of J4×4. In order to reduce those effects, heterodimer concentration was calculated from heterodimer stability and yielded an expression for predicting J4×4 for any salt, given approximately equal acid and base monomer concentrations and knowledge of monomer concentration and temperature. This parameterization was tested for the sulfuric acid–ammonia system by comparing the predicted values to experimental data and was found to be accurate within 2 orders of magnitude. We show that one can create a simple parameterization that incorporates the dependence on temperature and monomer concentration on J4×4 by defining a new term that we call the normalized heterodimer concentration, Φ. A plot of J4×4 vs. Φ collapses to a single monotonic curve for weak sulfate salts (difference in gas-phase acidity >95 kcal mol−1) and can be used to accurately estimate J4×4 within 2 orders of magnitude in atmospheric models.

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Section: Introductionmentioning

confidence: 99%

A predictive model for salt nanoparticle formation using heterodimer stability calculations

2021

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Section: Resultsmentioning

confidence: 99%

“…33 Moreover, we speculate that the added hydroxyl group can increase the hydrophilicity of the system as a hydrogen bond donor, while the carbonyl group is opposite. 103 TA may present higher enhancement to NPF involving SA and DMA than MA, which requires more experiments to verify.…”

Section: Resultsmentioning

confidence: 99%

“…On the other hand, compared to carboxylic acids without hydroxyl groups, clusters with more hydroxyl groups are likely more hydrophilic as more hydrogen bond donors and could further interact with other molecules to contribute to growth on both sides according to a previous study showing that water uptake by ammonium bisulfate clusters depends on the total number of free hydrogen bond donors in clusters 102 as well as for sulfuric acid-dimethylamine clusters. 103 For SUA and MA-containing system, the enhancement effect of OA under lower sulfuric acid concentration ([SA] o 8 Â 10 9 molecules cm À3 ) is higher than that under higher [SA] (that is, the formation rate is power dependent on SA, and the value becomes smaller) as shown in Fig. 3.…”

Section: And Lowermentioning

confidence: 93%

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Sulfuric acid–dimethylamine particle formation enhanced by functional organic acids: an integrated experimental and theoretical study

Wang

Liu

Huang

et al. 2022

Phys. Chem. Chem. Phys.

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“…This was demonstrated by our recent work where we found that formic acid is as effective as ammonia for the formation of clusters with sulfuric acid and water . Including water molecules results in the formation of hydrogen-bond networks. , Sulfuric acid can form comparably stable clusters with atmospheric species other than bases, such as formic acid , and amino acids. − In these cases, the ability of functional groups to form strong intermolecular interactions is key to the thermodynamic stability of the cluster. , Amino acids are enriched in sea spray aerosols by up to 7 orders of magnitude, and they are driven to the aerosol air–water interface in salts and acidic environments . At the interface, they are more reactive, including for the formation of peptide bonds. − Yet, amino acids without the presence of sulfuric acid do not drive aerosol formation .…”

Section: Introductionmentioning

confidence: 93%

Amino Acids Compete with Ammonia in Sulfuric Acid-Based Atmospheric Aerosol Prenucleation: The Case of Glycine and Serine

et al. 2022

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We present a computational investigation of the sulfuric acid, glycine, serine, ammonia, and water system to understand if this system can form prenucleation clusters, which are precursors to larger aerosols in the atmosphere. We have performed a comprehensive configurational search of all possible clusters in this system, starting with the four different monomers and zero to five waters. Accurate Gibbs free energies of formation have been calculated with the DLPNO-CCSD(T)/complete basis set (CBS) method on ωb97xd/6-31++G** geometries. For the dry dimers of sulfuric acid, the weakest base, serine, is found to form the most stable complex, which is a consequence of the strong di-ionic complex formed between the bisulfate ion and the protonated serine cation. For the dry dimers without sulfuric acid, the glycine–serine complex is more stable than the glycine–ammonia or serine–ammonia complexes, stemming from the detailed structure and not related to base strength. For the larger complexes, sulfuric acid deprotonates and the proton is shifted to glycine, serine, or ammonia. The two amino acids and ammonia are almost interchangeable and there is no easy way to predict which molecule will be protonated without the calculated results. Assuming reasonable starting concentrations and a closed system of sulfuric acid, glycine, serine, ammonia, and five waters, we predict the concentrations of all possible complexes at two temperatures spanning the troposphere. The most negative ΔG° values are a function of the detailed molecular interactions of these clusters. These details are more important than the base strength of ammonia, glycine, and serine.

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Molecular properties affecting the hydration of acid–base clusters

Abstract: In the atmosphere, water in all phases is ubiquitous and plays important roles in catalyzing atmospheric chemical reactions, participating in cluster formation and affecting the composition of aerosol particles. Direct...

Cited by 13 publications

References 58 publications

A predictive model for salt nanoparticle formation using heterodimer stability calculations

A predictive model for salt nanoparticle formation using heterodimer stability calculations

Sulfuric acid–dimethylamine particle formation enhanced by functional organic acids: an integrated experimental and theoretical study

Amino Acids Compete with Ammonia in Sulfuric Acid-Based Atmospheric Aerosol Prenucleation: The Case of Glycine and Serine

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