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Cluster Phase Chemistry: Gas-Phase Reactions of Anionic Sodium Salts of Dicarboxylic Acid Clusters with Water Molecules

Kim, Hugh I. and Goddard, William A., III and Beauchamp, J. L. (2006) Cluster Phase Chemistry: Gas-Phase Reactions of Anionic Sodium Salts of Dicarboxylic Acid Clusters with Water Molecules. Journal of Physical Chemistry A, 110 (25). pp. 7777-7786. ISSN 1089-5639. https://resolver.caltech.edu/CaltechAUTHORS:20170607-112622412

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Abstract

A homologous series of anionic gas-phase clusters of dicarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid) generated via electrospray ionization (ESI) are investigated using collision-induced dissociation (CID). Sodiated clusters with the composition (Na+)2n+1(dicarboxylate2-)n+1 for singly charged anionic clusters, where n = 1−4, are observed as major gas-phase species. Isolation of the clusters followed by CID results mainly in sequential loss of disodium dicarboxylate moieties for the clusters of succinic acid, glutaric acid, and adipic acid (C4−C6). However, all oxalate (C2) and malonate (C3) clusters and dimers (n = 1) of succinate (C4) and glutarate (C5) exhibit more complex chemistry initiated by collision of the activated cluster with water molecules. For example, with water addition, malonate clusters dissociate to yield sodium acetate, carbon dioxide, and sodium hydroxide. More generally, water molecules serve as proton donors for reacting dicarboxylate anions in the cluster and introduce energetically favorable dissociation pathways not otherwise available. Density functional theory (DFT) calculations of the binding energy of the cluster correlate well with the cluster phase reactions of oxalate and malonate clusters. Clusters of larger dicarboxylate ions (C4−C6) are more weakly bound, facilitating the sequential loss of disodium dicarboxylate moieties. The more strongly bound small dicarboxylate anions (oxalate and malonate) preferentially react with water molecules rather than dissociate to lose disodium dicarboxylate monomers when collisionally activated. Implications of these results for the atmospheric aerosol chemistry of dicarboxylic acids are discussed.


Item Type:Article
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URLURL TypeDescription
http://dx.doi.org/10.1021/jp055944vDOIArticle
ORCID:
AuthorORCID
Kim, Hugh I.0000-0002-6210-3107
Goddard, William A., III0000-0003-0097-5716
Beauchamp, J. L.0000-0001-8839-4822
Additional Information:© 2006 American Chemical Society. Received 17 October 2005. Published online 3 June 2006. Published in print 1 June 2006. The research described in this paper was carried out at the Beckman Institute and Jet Propulsion Laboratory of the California Institute of Technology. We appreciate the support provided by the Mass Spectrometry Resource Center in the Beckman Institute, California Institute of Technology. Partial support was also provided by the National Science Foundation (NSF) under grant no. CHE-0416381. We greatly appreciate the support and critical discussion of Drs. Isik Kanik, Luther W. Beegle, Paul V. Johnson, and Charles P. Malone at Jet Propulsion Laboratory, California Institute of Technology.
Funders:
Funding AgencyGrant Number
Caltech Beckman InstituteUNSPECIFIED
NSFCHE-0416381
Issue or Number:25
Record Number:CaltechAUTHORS:20170607-112622412
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170607-112622412
Official Citation:Cluster Phase Chemistry:  Gas-Phase Reactions of Anionic Sodium Salts of Dicarboxylic Acid Clusters with Water Molecules Hugh I. Kim, William A. Goddard III, and J. L. Beauchamp The Journal of Physical Chemistry A 2006 110 (25), 7777-7786 DOI: 10.1021/jp055944v
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:78003
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:07 Jun 2017 21:41
Last Modified:27 Feb 2020 23:53

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