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Fourier Transform Ultraviolet Spectroscopy of the A Pi-2(3/2) Direct Current X Pi-2(3/2) Transition of BrOThe first spectra of the A (2)Pi(sub 3/2) from X (2)Pi(sub 3/2) electronic transition of BrO using Fourier transform ultraviolet spectroscopy are obtained. Broadband vibrational spectra acquired at 298 +/- 2 K and 228 +/- 5 K, as well as high-resolution rotational spectra of the A from X 7,0 and 12,0 vibrational bands are presented. Wavenumber positions for the spectra are obtained with high accuracy, and cross section assignments are made, incorporating the existing literature. With 35 cm(exp -1) (0.40 nm) resolution the absolute cross section at the peak of the 7,0 band is determined to be (1.58 +/- 0.12) x 10(exp -17) sq cm/molecule at 298 +/- 2 K and (1.97 +/- 0.15) x 10(exp -17) sq cm/molecule at 228 +/- 5 K. BrO dissociation energies are determined with a graphical Birge-Sponer technique, using Le Roy-Bernstein theory to place an upper limit on the extrapolation. From the ground-state dissociation energy, D(sub o)" = 231.0 +/- 1.7 kJ/mol, the heat of formation of BrO(g) is calculated, del(sub f)H(0 K) = 133.7 +/- 1.7 kJ/mol and del(sub f)H(298.15 K) = 126.2 +/- 1.7 kJ/mol. Cross sections for the high-resolution 7,0 and 12,0 rotational peaks are the first to be reported. The band structures are modeled, and improved band origins, rotational constants, centrifugal distortion constants, and linewidths are determined. In particular, J-dependent linewidths and lifetimes are observed for the both the 7,0 and 12,0 bands.
Document ID
20010065902
Acquisition Source
Langley Research Center
Document Type
Reprint (Version printed in journal)
External Source(s)
Authors
Wilmouth, David M.
(Harvard Univ. Cambridge, MA United States)
Hanisco, Thomas F.
(Harvard Univ. Cambridge, MA United States)
Donahue, Neil M.
(Harvard Univ. Cambridge, MA United States)
Anderson, James G.
(Harvard Univ. Cambridge, MA United States)
Date Acquired
August 20, 2013
Publication Date
January 1, 1999
Publication Information
Publication: Journal of Physical Chemistry A
Publisher: American Chemical Society
Volume: 103
Issue: 45
Subject Category
Atomic And Molecular Physics
Funding Number(s)
CONTRACT_GRANT: NSF ATM-89-21312
CONTRACT_GRANT: NAG1-1305
Distribution Limits
Public
Copyright
Other

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