Atmospheric aerosol particles are commonly complex, aqueous organic-inorganic mixtures, and accurately predicting the properties of these particles is essential for air quality and climate projections. The prevailing assumption is that aqueous organic-inorganic aerosols exist predominately with liquid properties and that the hygroscopic inorganic fraction lowers aerosol viscosity relative to the organic fraction alone. Here, in contrast to those assumptions, we demonstrate that increasing inorganic fraction can increase aerosol viscosity (relative to predictions) and enable a humidity-dependent gel phase transition through cooperative ion-molecule interactions that give rise to long-range networks of atmospherically relevant low-mass oxygenated organic molecules (180 to 310 Da) and divalent inorganic ions. This supramolecular, ion-molecule effect can drastically influence the phase and physical properties of organic-inorganic aerosol and suggests that aerosol may be (semi)solid under more conditions than currently predicted. These observations, thus, have implications for air quality and climate that are not fully represented in atmospheric models.
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http://dx.doi.org/10.1126/sciadv.abb5643 | DOI Listing |
Phys Med
December 2024
Physics Dep., Sapienza U. of Rome, p.le Aldo Moro, 2, 00185, Rome, Italy; INFN, Sec. of Rome, p.le Aldo Moro, 2, 00185, Rome, Italy.
J Phys Chem A
December 2024
State Key Laboratory of Urban Water Resource and Environment, MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, P. R. China.
Precise prediction of reactivity and accurately identifying the types of reaction complexes are prerequisites for delineating the microscopic mechanisms of ion-molecule reactions, which remain unclear for reactions involving α-nucleophilic reagents. Here, we investigate the potential energy surface of the multiatomic reactions XO (X = F, *Cl, Br, I) + CHCHCl to elucidate the optimal descriptors for reaction reactivity and the origin of halogen bond/hydrogen bond compounds. Through analyzing the orbital composition and the relationship of energy barriers with the proton affinity and nucleophilic index, the local nucleophilic index is ultimately determined to be the optimal descriptor for predicting the reactivity of the reactions with α-nucleophilic reagents.
View Article and Find Full Text PDFJ Phys Chem A
August 2024
Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China.
The catalytic transformation of CO into valuable products has garnered wide interest owing to both economic and environmental benefits, in which the chemical fixation of CO into carbonate structures represents a crucial step that occurs on the adsorbed catalyst surfaces. Transition metal oxides with acidic and basic active sites have exhibited potential in promoting the carbonation of weakly bound CO molecules. Here, the interactions between CO molecules and the ScO cation in the gas phase are investigated by using infrared photodissociation spectroscopy in conjunction with quantum chemical calculations.
View Article and Find Full Text PDFJ Am Chem Soc
August 2024
FELIX Laboratory, Institute for Molecules and Materials, Radboud University, Nijmegen 6525 ED, The Netherlands.
Aromatic molecules play an important role in the chemistry of astronomical environments such as the cold interstellar medium (ISM) and (exo)planetary atmospheres. The observed abundances of (polycyclic) aromatic hydrocarbons such as benzonitrile and cyanonaphthalenes are, however, highly underestimated by astrochemical models. This demonstrates the need for more experimentally verified reaction pathways.
View Article and Find Full Text PDFEnviron Sci Atmos
July 2024
Carnegie Mellon University, Department of Chemistry Pittsburgh PA USA +1 412 268-4415.
Isoprene affects new particle formation rates in environments and experiments also containing monoterpenes. For the most part, isoprene reduces particle formation rates, but the reason is debated. It is proposed that due to its fast reaction with OH, isoprene may compete with larger monoterpenes for oxidants.
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