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Title: Sum frequency generation of O-H vibrations on the surface of H{sub 2}O/HNO{sub 3} solutions and liquid HNO{sub 3}

Abstract

The surfaces of aqueous HNO{sub 3} solutions and liquid HNO{sub 3} are examined using sum frequency generation (SFG). A molecular-level picture of these atmospherically relevant systems is developed. Consistent with previous interpretations, an electric double layer comprised of subsurface anions and cations develops in 0.005x and 0.01x HNO{sub 3} solutions, where x = mole fraction. Compared to pure water, these solutions generate more SFG signal in the hydrogen-bonded region as water molecules respond to the subsurface electric field by aligning with the surface normal. At higher concentrations, 0.05x and 0.4x HNO{sub 3}, ionic complexes or molecules sufficiently approach the surface to disrupt the hydrogen-bonding network and perturb the first water layer. Neither liquid nitric acid nor its solutions show a clear O-H.

Authors:
; ; ;
Publication Date:
Research Org.:
Tufts Univ., Medford, MA (US)
OSTI Identifier:
20000058
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
Additional Journal Information:
Journal Volume: 103; Journal Issue: 32; Other Information: PBD: 12 Aug 1999; Journal ID: ISSN 1089-5639
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; NITRIC ACID; AQUEOUS SOLUTIONS; ATMOSPHERIC CHEMISTRY; INFRARED SPECTRA; LASERS; MATHEMATICAL MODELS; EXPERIMENTAL DATA; THEORETICAL DATA; RAMAN SPECTRA

Citation Formats

Schnitzer, C., Baldelli, S., Campbell, D.J., and Shultz, M.J. Sum frequency generation of O-H vibrations on the surface of H{sub 2}O/HNO{sub 3} solutions and liquid HNO{sub 3}. United States: N. p., 1999. Web. doi:10.1021/jp9908956.
Schnitzer, C., Baldelli, S., Campbell, D.J., & Shultz, M.J. Sum frequency generation of O-H vibrations on the surface of H{sub 2}O/HNO{sub 3} solutions and liquid HNO{sub 3}. United States. doi:10.1021/jp9908956.
Schnitzer, C., Baldelli, S., Campbell, D.J., and Shultz, M.J. Thu . "Sum frequency generation of O-H vibrations on the surface of H{sub 2}O/HNO{sub 3} solutions and liquid HNO{sub 3}". United States. doi:10.1021/jp9908956.
@article{osti_20000058,
title = {Sum frequency generation of O-H vibrations on the surface of H{sub 2}O/HNO{sub 3} solutions and liquid HNO{sub 3}},
author = {Schnitzer, C. and Baldelli, S. and Campbell, D.J. and Shultz, M.J.},
abstractNote = {The surfaces of aqueous HNO{sub 3} solutions and liquid HNO{sub 3} are examined using sum frequency generation (SFG). A molecular-level picture of these atmospherically relevant systems is developed. Consistent with previous interpretations, an electric double layer comprised of subsurface anions and cations develops in 0.005x and 0.01x HNO{sub 3} solutions, where x = mole fraction. Compared to pure water, these solutions generate more SFG signal in the hydrogen-bonded region as water molecules respond to the subsurface electric field by aligning with the surface normal. At higher concentrations, 0.05x and 0.4x HNO{sub 3}, ionic complexes or molecules sufficiently approach the surface to disrupt the hydrogen-bonding network and perturb the first water layer. Neither liquid nitric acid nor its solutions show a clear O-H.},
doi = {10.1021/jp9908956},
journal = {Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory},
issn = {1089-5639},
number = 32,
volume = 103,
place = {United States},
year = {1999},
month = {8}
}