Size-Dependent Onset of Nitric Acid Dissociation in Cs+·(HNO3)(H2O)n=0–11 Clusters at 20 K
Abstract
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.
- Authors:
-
- 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)
- Publication Date:
- Research Org.:
- Yale Univ., New Haven, CT (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1773044
- Grant/Contract Number:
- SC0021012; FG02-06ER15800; NA0003525
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Volume: 12; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Acid dissociation; Mass spectrometry; Infrared spectroscopy
Citation Formats
Mitra, Sayoni, Yang, Nan, McCaslin, Laura M., Gerber, R. Benny, and Johnson, Mark A. Size-Dependent Onset of Nitric Acid Dissociation in Cs+·(HNO3)(H2O)n=0–11 Clusters at 20 K. United States: N. p., 2021.
Web. doi:10.1021/acs.jpclett.1c00235.
Mitra, Sayoni, Yang, Nan, McCaslin, Laura M., Gerber, R. Benny, & Johnson, Mark A. Size-Dependent Onset of Nitric Acid Dissociation in Cs+·(HNO3)(H2O)n=0–11 Clusters at 20 K. United States. https://doi.org/10.1021/acs.jpclett.1c00235
Mitra, Sayoni, Yang, Nan, McCaslin, Laura M., Gerber, R. Benny, and Johnson, Mark A. Mon .
"Size-Dependent Onset of Nitric Acid Dissociation in Cs+·(HNO3)(H2O)n=0–11 Clusters at 20 K". United States. https://doi.org/10.1021/acs.jpclett.1c00235. https://www.osti.gov/servlets/purl/1773044.
@article{osti_1773044,
title = {Size-Dependent Onset of Nitric Acid Dissociation in Cs+·(HNO3)(H2O)n=0–11 Clusters at 20 K},
author = {Mitra, Sayoni and Yang, Nan and McCaslin, Laura M. and Gerber, R. Benny and Johnson, Mark A.},
abstractNote = {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.},
doi = {10.1021/acs.jpclett.1c00235},
journal = {Journal of Physical Chemistry Letters},
number = ,
volume = 12,
place = {United States},
year = {Mon Mar 29 00:00:00 EDT 2021},
month = {Mon Mar 29 00:00:00 EDT 2021}
}
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