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Quantum chemical insights into the dissociation of nitric acid on the surface of aqueous electrolytes

Mishra, Himanshu and Nielsen, Robert J. and Enami, Shinichi and Hoffmann, Michael R. and Colussi, Agustín J. and Goddard, William A., III (2013) Quantum chemical insights into the dissociation of nitric acid on the surface of aqueous electrolytes. International Journal of Quantum Chemistry, 113 (4). pp. 413-417. ISSN 0020-7608.

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Recent experiments in our laboratory have shown that the probability of gaseous HNO_3 deprotonation on the surface of water is dramatically enhanced by anions. Herein, we report a quantum chemical study of how a HNO_3 molecule transfers its proton upon approaching water clusters containing or not a chloride ion. We find that HNO_3 always binds to the outermost water molecules both via donating and accepting hydrogen-bonds, but the free energy barrier for subsequent proton transfer into the clusters is greatly reduced in the presence of Cl^−. As the dissociation of HNO_3 embedded in water clusters is barrierless, we infer that interfacial proton transfer to water is hindered by the cost of creating a cavity for NO_(3)^−. Our findings suggest that nearby anions catalyze HNO_3 dissociation by preorganizing interfacial water and drawing the proton—away from the incipient [H^(+)---NO_(3)^−] close ion-pairs generated at the interface. This catalytic mechanism would operate in the 1 mM Cl^− range (1 Cl− in ∼5.5 × 10^4 water molecules) covered by our experiments if weakly adsorbed HNO_3 were able to explore extended surface domains before desorbing or diffusing (undissociated) into bulk water.

Item Type:Article
Related URLs:
URLURL TypeDescription
Nielsen, Robert J.0000-0002-7962-0186
Enami, Shinichi0000-0002-2790-7361
Hoffmann, Michael R.0000-0001-6495-1946
Colussi, Agustín J.0000-0002-3400-4101
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2012 Wiley Periodicals, Inc. Issue published online: 22 January 2013; Article first published online: 31 May 2012; Manuscript Accepted: 9 April 2012; Manuscript Revised: 6 April 2012; Manuscript Received: 15 January 2012. This research was supported partially by a grant from the National Science Foundation to M.R.H. (NSF Grant AGS-964842).
Funding AgencyGrant Number
Subject Keywords:nitric acid dissociation; proton transfers at aqueous interfaces; electrostatic preorganization; interfacial anions; air–water interface
Issue or Number:4
Record Number:CaltechAUTHORS:20130301-100027846
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Official Citation:H. Mishra, RJ. Nielsen, S. Enami, MR. Hoffmann, AJ. Colussi, WA. GoddardIII, Int. J. Quantum Chem. 2013, 113, 413–417. DOI: 10.1002/qua.24151
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:37230
Deposited By: Jason Perez
Deposited On:01 Mar 2013 21:46
Last Modified:03 Mar 2020 13:01

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