Growth of Ammonium Bisulfate Clusters by Adsorption of Oxygenated Organic Molecules.
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.
Department of Chemistry and Biochemistry, University of Delaware , Newark, Delaware 19716, United States.
Joseph W
JW
DePalma
Biological, Environmental & Climate Sciences Department, Brookhaven National Laboratory , Upton, New York 11973-5000, United States.
Jian
J
Wang
Departments of Mechanical and Aerospace Engineering, Civil and Environmental Engineering and Land, Air and Water Resources, University of California, Davis , Davis, California 95616, United States.
Anthony S
AS
Wexler
Department of Chemistry and Biochemistry, University of Delaware , Newark, Delaware 19716, United States.
Murray V
MV
Johnston
D000327:Adsorption; D000447:Aldehydes / Q000737:chemistry*; D000645:Ammonium Sulfate / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D006860:Hydrogen Bonding; D007659:Ketones / Q000737:chemistry*; D008956:Models, Chemical; D010084:Oxidation-Reduction; D011789:Quantum Theory; D013816:Thermodynamics
D000447:Aldehydes; D002264:Carboxylic Acids; D007659:Ketones; C034007:ammonium bisulfate; D000645:Ammonium Sulfate