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 language | English (US) |
|---|---|
| Pages (from-to) | 11191-11198 |
| Number of pages | 8 |
| Journal | Journal of Physical Chemistry A |
| Volume | 119 |
| Issue number | 45 |
| DOIs | |
| State | Published - Oct 21 2015 |
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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 journal › Article
}
TY - JOUR
T1 - Growth of Ammonium Bisulfate Clusters by Adsorption of Oxygenated Organic Molecules
AU - DePalma, Joseph W.
AU - Wang, Jian
AU - Wexler, Anthony S.
AU - Johnston, Murray V.
PY - 2015/10/21
Y1 - 2015/10/21
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84946866399&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84946866399&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.5b07744
DO - 10.1021/acs.jpca.5b07744
M3 - Article
C2 - 26488562
AN - SCOPUS:84946866399
VL - 119
SP - 11191
EP - 11198
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 45
ER -