Size-Dependent Onset of Nitric Acid Dissociation in Cs+·(HNO3)(H2O)n=0–11 Clusters at 20 K

Mitra, Sayoni; Yang, Nan; McCaslin, Laura M.; Gerber, R. Benny; Johnson, Mark A.

doi:10.1021/acs.jpclett.1c00235

Size-Dependent Onset of Nitric Acid Dissociation in Cs⁺·(HNO₃)(H₂O)_n=0–11 Clusters at 20 K

Journal Article · Mon Mar 29 04:00:00 EDT 2021 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.1c00235· OSTI ID:1773044

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Yale Univ., New Haven, CT (United States); Yale University
Yale Univ., New Haven, CT (United States)
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
The Hebrew Univ., Jerusalem (Israel); Univ. of California, Irvine, CA (United States)

We report the water-mediated charge separation of nitric acid upon incorporation into size-selected Cs⁺∙(HNO₃)(H₂O)_n=0-11 clusters at 20 K. Dramatic spectral changes are observed in the range n=7-9 that are traced to the formation of many isomeric structures associated with intermediate transfer of the acidic proton to the water network. This transfer is complete by n=10, which exhibits much simpler vibrational band patterns consistent with those expected for a tri-coordinated hydronium ion (the Eigen motif) along with the NO stretching bands predicted for a hydrated NO₃^– anion that is directly complexed to the Cs⁺ cation. Theoretical analysis of the n=10 spectrum indicates that the dissociated ions adopt a solvent-separated ion-pair configuration such that the Cs⁺ and H₃O⁺ cations flank the NO₃^– anion in a microhydrated salt bridge. In conclusion, this charge separation motif is evidently assisted by the electrostatic stabilization of the product NO₃^–/H₃O⁺ ion pair by the proximal metal ion.

View Accepted Manuscript (DOE)

Research Organization:: Yale Univ., New Haven, CT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: SC0021012; FG02-06ER15800; NA0003525

OSTI ID:: 1773044

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Vol. 12; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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