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

Mitra, Sayoni; Khuu, Thien; Choi, Tae Hoon; Huchmala, Rachel M.; Jordan, Kenneth D.; McCoy, Anne B.; Johnson, Mark Albert

doi:10.1021/acs.jpca.1c10352

Title: 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 · 04 March 2022 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI: https://doi.org/10.1021/acs.jpca.1c10352 · OSTI ID:1846571

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Yale Univ., New Haven, CT (United States); Yale University
Yale Univ., New Haven, CT (United States)
Univ. of Pittsburgh, PA (United States)
Univ. of Washington, Seattle, WA (United States)

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.

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

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Engineering & Technology

Grant/Contract Number:: SC0021012

OSTI ID:: 1846571

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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Title: 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

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Title: 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