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Vibrational signatures of HNO3 acidity when complexed with microhydrated alkali metal ions, M+∙(HNO3)(H2O)n=5 (M = Li, K, Na, Rb, Cs), at 20 K

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [2];  [3];  [4];  [3];  [4];  [2]
  1. Yale Univ., New Haven, CT (United States); Yale University
  2. Yale Univ., New Haven, CT (United States)
  3. Univ. of Pittsburgh, PA (United States)
  4. Univ. of Washington, Seattle, WA (United States)
+ Show Author Affiliations
The speciation of strong acids like HNO3 under conditions of restricted hydration is an important factor in the rates of chemical reactions at the air-water interface. Here we explore the trade-offs in play when HNO3 is attached to alkali ions (Li+-Cs+) with four water molecules in their primary hydration shells. This is achieved by analyzing the vibrational spectra of the M+∙(HNO3)(H2O)5 clusters cooled to about 20 K in a cryogenic photofragmentation mass spectrometer. The local acidity of the acidic OH group is estimated by the extent of the red shift in its stretching frequency when attached to a single water molecule. Here, the persistence of this local structural motif (HNO3-H2O) in all of these alkali metal clusters enables us to determine the competition between the effect of the direct complexation of the acid with the cation, which acts to enhance acidity, and the role of the water network in the first hydration shell around the ions, which acts to counter (screen) the intrinsic effect of the ion. Analysis of the vibrational features associated with the acid molecule as well as those of the water network reveal how cooperative interactions in the micro hydration regime conspire to effectively offset the intrinsic enhancement of HNO3 acidity afforded by attachment to the smaller cations.
Research Organization:
Yale Univ., New Haven, CT (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Engineering & Technology
Grant/Contract Number:
SC0021012
OSTI ID:
1846571
Alternate ID(s):
OSTI ID: 1855570
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 10 Vol. 126; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Cluster chemistry
Hydration
Ions
Molecular structure
Molecules