Cluster phase chemistry

Gas-phase reactions of anionic sodium salts of dicarboxylic acid clusters with water molecules

Hugh I. Kim, William A. Goddard, J. L. Beauchamp

Research output: Contribution to journalArticle

16 Citations (Scopus)

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(dicarboxylate 2-) 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.

Original languageEnglish
Pages (from-to)7777-7786
Number of pages10
JournalJournal of Physical Chemistry A
Volume110
Issue number25
DOIs
Publication statusPublished - 2006 Jun 29
Externally publishedYes

Fingerprint

Dicarboxylic Acids
dicarboxylic acids
Salts
Gases
Sodium
sodium
Oxalates
chemistry
vapor phases
salts
Succinic Acid
Molecules
Water
water
molecules
Anions
acids
Glutarates
Oxalic Acid
Sodium Acetate

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Cluster phase chemistry : Gas-phase reactions of anionic sodium salts of dicarboxylic acid clusters with water molecules. / Kim, Hugh I.; Goddard, William A.; Beauchamp, J. L.

In: Journal of Physical Chemistry A, Vol. 110, No. 25, 29.06.2006, p. 7777-7786.

Research output: Contribution to journalArticle

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