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Title: Absolute intensities for third and fourth overtone absorptions in HNO{sub 3} and H{sub 2}O{sub 2} measured by cavity ring down spectroscopy

Abstract

Photodissociation of nitric acid and hydrogen peroxide via high-lying O-H overtone absorptions in the visible may act as a source of OH radicals in the atmosphere. The authors have used cavity ring down spectroscopy to measure the absorption cross sections for the third (4{nu}{sub OH}) and fourth (5{nu}{sub OH}) overtone transitions in these molecules. The integrated cross sections are (2.25 {+-} 0.15) x 10{sup {minus}21} and (2.57 {+-} 0.24) x 10{sup {minus}22} cm{sup 2} molecule{sup {minus}1} cm{sup {minus}1} for 4{nu}{sub OH} and 5{nu}{sub OH} in nitric acid, respectively, and (4.58 {+-} 0.39) x 10{sup {minus}21} and (5.67 {+-} 0.52) x 10{sup {minus}22} cm{sup 2} molecule{sup {minus}1} cm{sup {minus}1} for 4{nu}{sub OH} and 5{nu}{sub OH} in hydrogen peroxide. For both molecules, their report is the first direct intensity measurement for 5{nu}{sub OH}, the lowest dissociative overtone transition. The authors compare their values for the lower overtones to those from previous studies, where available. Measured cross sections suggest that the contribution of direct overtone excitation to the atmospheric photodissociation of HNO{sub 3} and H{sub 2}O{sub 2} is small but not completely negligible.

Authors:
; ;
Publication Date:
Research Org.:
National Oceanic and Atmospheric Administration, Boulder, CO (US)
OSTI Identifier:
20075886
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
Additional Journal Information:
Journal Volume: 104; Journal Issue: 21; Other Information: PBD: 1 Jun 2000; Journal ID: ISSN 1089-5639
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; NITRIC ACID; HYDROGEN PEROXIDE; PHOTOCHEMISTRY; ATMOSPHERIC CHEMISTRY; DISSOCIATION; MICROWAVE SPECTRA

Citation Formats

Brown, S.S., Wilson, R.W., and Ravishankara, A.R. Absolute intensities for third and fourth overtone absorptions in HNO{sub 3} and H{sub 2}O{sub 2} measured by cavity ring down spectroscopy. United States: N. p., 2000. Web. doi:10.1021/jp000439d.
Brown, S.S., Wilson, R.W., & Ravishankara, A.R. Absolute intensities for third and fourth overtone absorptions in HNO{sub 3} and H{sub 2}O{sub 2} measured by cavity ring down spectroscopy. United States. doi:10.1021/jp000439d.
Brown, S.S., Wilson, R.W., and Ravishankara, A.R. Thu . "Absolute intensities for third and fourth overtone absorptions in HNO{sub 3} and H{sub 2}O{sub 2} measured by cavity ring down spectroscopy". United States. doi:10.1021/jp000439d.
@article{osti_20075886,
title = {Absolute intensities for third and fourth overtone absorptions in HNO{sub 3} and H{sub 2}O{sub 2} measured by cavity ring down spectroscopy},
author = {Brown, S.S. and Wilson, R.W. and Ravishankara, A.R.},
abstractNote = {Photodissociation of nitric acid and hydrogen peroxide via high-lying O-H overtone absorptions in the visible may act as a source of OH radicals in the atmosphere. The authors have used cavity ring down spectroscopy to measure the absorption cross sections for the third (4{nu}{sub OH}) and fourth (5{nu}{sub OH}) overtone transitions in these molecules. The integrated cross sections are (2.25 {+-} 0.15) x 10{sup {minus}21} and (2.57 {+-} 0.24) x 10{sup {minus}22} cm{sup 2} molecule{sup {minus}1} cm{sup {minus}1} for 4{nu}{sub OH} and 5{nu}{sub OH} in nitric acid, respectively, and (4.58 {+-} 0.39) x 10{sup {minus}21} and (5.67 {+-} 0.52) x 10{sup {minus}22} cm{sup 2} molecule{sup {minus}1} cm{sup {minus}1} for 4{nu}{sub OH} and 5{nu}{sub OH} in hydrogen peroxide. For both molecules, their report is the first direct intensity measurement for 5{nu}{sub OH}, the lowest dissociative overtone transition. The authors compare their values for the lower overtones to those from previous studies, where available. Measured cross sections suggest that the contribution of direct overtone excitation to the atmospheric photodissociation of HNO{sub 3} and H{sub 2}O{sub 2} is small but not completely negligible.},
doi = {10.1021/jp000439d},
journal = {Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory},
issn = {1089-5639},
number = 21,
volume = 104,
place = {United States},
year = {2000},
month = {6}
}