Hydration of Atmospheric Molecular Clusters II: Organic Acid–Water Clusters

Jens Vive Kildgaard; Kurt Valentin Mikkelsen; Merete Bilde; Jonas Elm

doi:10.1021/acs.jpca.8b07713

Hydration of Atmospheric Molecular Clusters II: Organic Acid–Water Clusters

Jens Vive Kildgaard, Kurt Valentin Mikkelsen, Merete Bilde, Jonas Elm

Department of Chemistry

21 Citations (Scopus)

Abstract

Using computational methods, we study the gas phase hydration of three different atmospherically relevant organic acids with up to 10 water molecules. We study a dicarboxylic acid (pinic acid) and a tricarboxylic acid (3-methyl-1,2,3-butanetricarboxylic acid (mbtca)) that are both identified as products from α-pinene oxidation reactions. We also study a 2-oxohexanediperoxy acid (ohdpa) that has been identified as a product from cyclohexene autoxidation. To sample the cluster structures, we employ our recently developed systematic hydrate sampling technique and identify a total of 551 hydrate clusters. The cluster structures and thermochemical parameters (at 298.15 K and 1 atm) are obtained at the ωB97X-D/6-31++G(d,p) level of theory, and the single point energy of the clusters have been refined using a high level DLPNO-CCSD(T)/aug-cc-pVTZ calculation. We find that all three tested organic acids interact significantly more weakly with water compared to the primary nucleation precursor sulfuric acid. Even at 100% relative humidity (298.15 K and 1 atm), we find that ohdpa remains unhydrated and only the monohydrate of pinic acid and mbtca are slightly populated (4% and 2%, respectively). From the obtained molecular structures, potential implications for the ice nucleating ability of aerosol particles is discussed.

Original language	English
Journal	Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Volume	122
Issue number	43
Pages (from-to)	8549–8556
Number of pages	8
ISSN	1089-5639
DOIs	https://doi.org/10.1021/acs.jpca.8b07713
Publication status	Published - 1 Nov 2018

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Hydration of Atmospheric Molecular Clusters II : Organic Acid–Water Clusters. / Kildgaard, Jens Vive; Mikkelsen, Kurt Valentin; Bilde, Merete et al.

In: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Vol. 122, No. 43, 01.11.2018, p. 8549–8556.

Research output: Contribution to journal › Journal article › Research › peer-review

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abstract = "Using computational methods, we study the gas phase hydration of three different atmospherically relevant organic acids with up to 10 water molecules. We study a dicarboxylic acid (pinic acid) and a tricarboxylic acid (3-methyl-1,2,3-butanetricarboxylic acid (mbtca)) that are both identified as products from α-pinene oxidation reactions. We also study a 2-oxohexanediperoxy acid (ohdpa) that has been identified as a product from cyclohexene autoxidation. To sample the cluster structures, we employ our recently developed systematic hydrate sampling technique and identify a total of 551 hydrate clusters. The cluster structures and thermochemical parameters (at 298.15 K and 1 atm) are obtained at the ωB97X-D/6-31++G(d,p) level of theory, and the single point energy of the clusters have been refined using a high level DLPNO-CCSD(T)/aug-cc-pVTZ calculation. We find that all three tested organic acids interact significantly more weakly with water compared to the primary nucleation precursor sulfuric acid. Even at 100% relative humidity (298.15 K and 1 atm), we find that ohdpa remains unhydrated and only the monohydrate of pinic acid and mbtca are slightly populated (4% and 2%, respectively). From the obtained molecular structures, potential implications for the ice nucleating ability of aerosol particles is discussed.",

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AU - Elm, Jonas

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N2 - Using computational methods, we study the gas phase hydration of three different atmospherically relevant organic acids with up to 10 water molecules. We study a dicarboxylic acid (pinic acid) and a tricarboxylic acid (3-methyl-1,2,3-butanetricarboxylic acid (mbtca)) that are both identified as products from α-pinene oxidation reactions. We also study a 2-oxohexanediperoxy acid (ohdpa) that has been identified as a product from cyclohexene autoxidation. To sample the cluster structures, we employ our recently developed systematic hydrate sampling technique and identify a total of 551 hydrate clusters. The cluster structures and thermochemical parameters (at 298.15 K and 1 atm) are obtained at the ωB97X-D/6-31++G(d,p) level of theory, and the single point energy of the clusters have been refined using a high level DLPNO-CCSD(T)/aug-cc-pVTZ calculation. We find that all three tested organic acids interact significantly more weakly with water compared to the primary nucleation precursor sulfuric acid. Even at 100% relative humidity (298.15 K and 1 atm), we find that ohdpa remains unhydrated and only the monohydrate of pinic acid and mbtca are slightly populated (4% and 2%, respectively). From the obtained molecular structures, potential implications for the ice nucleating ability of aerosol particles is discussed.

AB - Using computational methods, we study the gas phase hydration of three different atmospherically relevant organic acids with up to 10 water molecules. We study a dicarboxylic acid (pinic acid) and a tricarboxylic acid (3-methyl-1,2,3-butanetricarboxylic acid (mbtca)) that are both identified as products from α-pinene oxidation reactions. We also study a 2-oxohexanediperoxy acid (ohdpa) that has been identified as a product from cyclohexene autoxidation. To sample the cluster structures, we employ our recently developed systematic hydrate sampling technique and identify a total of 551 hydrate clusters. The cluster structures and thermochemical parameters (at 298.15 K and 1 atm) are obtained at the ωB97X-D/6-31++G(d,p) level of theory, and the single point energy of the clusters have been refined using a high level DLPNO-CCSD(T)/aug-cc-pVTZ calculation. We find that all three tested organic acids interact significantly more weakly with water compared to the primary nucleation precursor sulfuric acid. Even at 100% relative humidity (298.15 K and 1 atm), we find that ohdpa remains unhydrated and only the monohydrate of pinic acid and mbtca are slightly populated (4% and 2%, respectively). From the obtained molecular structures, potential implications for the ice nucleating ability of aerosol particles is discussed.

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JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

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ER -

Hydration of Atmospheric Molecular Clusters II: Organic Acid–Water Clusters

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