Sum Frequency Generation of O−H Vibrations on the Surface of H2O/HNO3 Solutions and Liquid HNO3

The surfaces of aqueous HNO3 solutions and liquid HNO3 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 de...

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Veröffentlicht in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 1999-08, Vol.103 (32), p.6383-6386
Hauptverfasser: Schnitzer, Cheryl, Baldelli, Steve, Campbell, D. J, Shultz, Mary Jane
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container_issue 32
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container_title The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory
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creator Schnitzer, Cheryl
Baldelli, Steve
Campbell, D. J
Shultz, Mary Jane
description The surfaces of aqueous HNO3 solutions and liquid HNO3 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 HNO3 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 HNO3, 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.
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title Sum Frequency Generation of O−H Vibrations on the Surface of H2O/HNO3 Solutions and Liquid HNO3
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