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

Himanshu Mishra, Robert J. Nielsen, Shinichi Enami, Michael R. Hoffmann, Agustín J. Colussi, William A. Goddard*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

13 Scopus citations


Recent experiments in our laboratory have shown that the probability of gaseous HNO3 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 HNO3 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 HNO3 embedded in water clusters is barrierless, we infer that interfacial proton transfer to water is hindered by the cost of creating a cavity for NO3-. Our findings suggest that nearby anions catalyze HNO3 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 × 104 water molecules) covered by our experiments if weakly adsorbed HNO3 were able to explore extended surface domains before desorbing or diffusing (undissociated) into bulk water.

Original languageEnglish (US)
Pages (from-to)413-417
Number of pages5
JournalInternational Journal of Quantum Chemistry
Issue number4
StatePublished - Feb 15 2013
Externally publishedYes


  • air-water interface
  • electrostatic preorganization
  • interfacial anions
  • nitric acid dissociation
  • proton transfers at aqueous interfaces

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry


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