Growth of Ammonium Bisulfate Clusters by Adsorption of Oxygenated Organic Molecules

Joseph W. DePalma, Jian Wang, Anthony S. Wexler, Murray V. Johnston

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

Quantum chemical calculations were employed to model the interactions of the [(NH4 +)4(HSO4 -)4] ammonium bisulfate cluster with one or more molecular products of monoterpene oxidation. A strong interaction was found between the bisulfate ion of this cluster and a carboxylic acid, aldehyde, or ketone functionality of the organic molecule. Free energies of adsorption for carboxylic acids were in the -70 to -73 kJ/mol range, while those for aldehydes and ketones were in the -46 to -50 kJ/mol range. These values suggest that a small ambient [(NH4 +)4(SO4 -)4]cluster is able to adsorb an oxygenated organic molecule. While adsorption of the first molecule is highly favorable, adsorption of subsequent molecules is less so, suggesting that sustained uptake of organic molecules does not occur, and thus is not a pathway for continuing growth of the cluster. This result is consistent with ambient measurements showing that particles below ∼1 nm grow slowly, while those above 1 nm grow at an increasing rate presumably due to a lower surface energy barrier enabling the uptake of organic molecules. This work provides insight into the molecular level interactions which affect sustained cluster growth by uptake of organic molecules.

Original languageEnglish (US)
Pages (from-to)11191-11198
Number of pages8
JournalJournal of Physical Chemistry A
Volume119
Issue number45
DOIs
StatePublished - Oct 21 2015

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Adsorption
Molecules
adsorption
molecules
Carboxylic Acids
Ketones
aldehydes
Aldehydes
carboxylic acids
ketones
Monoterpenes
Energy barriers
ammonium bisulfate
Interfacial energy
Free energy
surface energy
free energy
interactions
Ions
Oxidation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Growth of Ammonium Bisulfate Clusters by Adsorption of Oxygenated Organic Molecules. / DePalma, Joseph W.; Wang, Jian; Wexler, Anthony S.; Johnston, Murray V.

In: Journal of Physical Chemistry A, Vol. 119, No. 45, 21.10.2015, p. 11191-11198.

Research output: Contribution to journalArticle

DePalma, Joseph W. ; Wang, Jian ; Wexler, Anthony S. ; Johnston, Murray V. / Growth of Ammonium Bisulfate Clusters by Adsorption of Oxygenated Organic Molecules. In: Journal of Physical Chemistry A. 2015 ; Vol. 119, No. 45. pp. 11191-11198.
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