University of Oulu

Hyttinen, N., Prisle, N. (2020) Improving Solubility and Activity Estimates of Multifunctional Atmospheric Organics by Selecting Conformers in COSMOtherm. Journal of Physical Chemistry A, 124 (23), 4801-4812. https://doi.org/10.1021/acs.jpca.0c04285

Improving solubility and activity estimates of multifunctional atmospheric organics by selecting conformers in COSMOtherm

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Author: Hyttinen, Noora1; Prisle, Nønne L.1
Organizations: 1Nano and Molecular Systems Research Unit, University of Oulu, 90014 Oulu, Finland
Format: article
Version: published version
Access: open
Online Access: PDF Full Text (PDF, 2.5 MB)
Persistent link: http://urn.fi/urn:nbn:fi-fe2020061744828
Language: English
Published: American Chemical Society, 2020
Publish Date: 2020-06-17
Description:

Abstract

We estimated aqueous solubilities and activity coefficients of atmospherically relevant highly oxidized multifunctional organic compounds in binary mixtures with water at temperatures between 278.15 and 338.15 K, using the COSMOtherm program. Physicochemical properties of organic aerosol constituents are needed in the modeling of atmospheric aerosol processes. As experimental data are often impossible to obtain, reliable estimates from theoretical approaches are a promising path to fill this gap. We investigated the effect of intramolecular hydrogen bonds on the estimation of these condensed-phase properties, attempting to improve the agreement between experimental and estimated values. Citric, tartaric, malic, and maleic acids, which are often used in atmospheric models as representatives of oxidized compounds, were selected to benchmark our calculations. In addition, we estimated aqueous solubilities and activity coefficients of α-pinene-derived organosulfates and highly oxidized isoprene-derived organic compounds, for which no experimental data are available. Our results indicate that the absolute aqueous solubility and activity coefficient estimates of citric, tartaric, malic, and maleic acids, and likely other multifunctional organics, can be improved significantly by selecting conformers on the basis of their intramolecular hydrogen bonding in COSMOtherm calculations.

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Series: The journal of physical chemistry. A
ISSN: 1089-5639
ISSN-E: 1520-5215
ISSN-L: 1089-5639
Volume: 124
Issue: 23
Pages: 4801 - 4812
DOI: 10.1021/acs.jpca.0c04285
OADOI: https://oadoi.org/10.1021/acs.jpca.0c04285
Type of Publication: A1 Journal article – refereed
Field of Science: 114 Physical sciences
116 Chemical sciences
Subjects:
Funding: This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme, Project SURFACE (Grant Agreement No. 717022). The authors also gratefully acknowledge the financial contribution from the Academy of Finland, including Grant No. 308238 and 314175.
EU Grant Number: (717022) SURFACE - The unexplored world of aerosol surfaces and their impacts.
Academy of Finland Grant Number: 308238
314175
Detailed Information: 308238 (Academy of Finland Funding decision)
314175 (Academy of Finland Funding decision)
Dataset Reference: The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpca.0c04285.
  https://pubs.acs.org/doi/10.1021/acs.jpca.0c04285
Copyright information: © 2020 American Chemical Society. This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
  https://creativecommons.org/licenses/by/4.0/