OH-Stretch Vibrational Spectroscopy of Hydroxymethyl Hydroperoxide
Abstract
We report measurement and analysis of the photodissociation spectrum of hydroxymethyl hydroperoxide (HOCH_2OOH) and its partially deuterated analogue, HOCD_2OOH, in the OH-stretching region. Spectra are obtained by Fourier transform infrared spectroscopy in the 1ν_(OH) and 2ν_(OH) regions, and by laser induced fluorescence detection of the OH fragment produced from dissociation of HOCH_2OOH initiated by excitation of the 4ν_(OH) and 5ν_(OH) overtone regions (action spectroscopy). A one-dimensional local-mode model of each OH chromophore is used with ab initio calculated OH-stretching potential energy and dipole moment curves at the coupled-cluster level of theory. Major features in the observed absorption and photodissociation spectra are explained by our local-mode model. In the 4ν_(OH) region, explanation of the photodissocation spectrum requires a nonuniform quantum yield, which is estimated by assuming statistical energy distribution in the excited state. Based on the estimated dissociation threshold, overtone photodissociation is not expected to significantly influence the atmospheric lifetime of hydroxymethyl hydroperoxide.
Additional Information
© 2006 American Chemical Society. Received: February 25, 2006; In Final Form: April 12, 2006. Publication Date (Web): May 17, 2006. The authors thank Mitchio Okumura, Daniel Schofield, Daryl Howard, and John Barker for valuable discussions. J.L.F. gratefully acknowledges funding provided by an American Association of University Women Dissertation Fellowship, and J.R.L. gratefully acknowledges a Top Achiever Doctoral scholarship from the Tertiary Education Commission. Funding for this work was provided by grants to P.O.W. from the National Science Foundation Division of Atmospheric Sciences (Grant ATM-0432377), to A.S. from the National Science Foundation Division of Chemistry (Grant CHE-0211496), and to H.G.K. from the Marsden Fund administered by the Royal Society of New Zealand. P.O.W. thanks the Department of Chemistry, Otago University, for support during sabbatical leave.Attached Files
Supplemental Material - jp0612127si20060225_122329.txt
Supplemental Material - jp0612127si20060225_122400.txt
Supplemental Material - jp0612127si20060412_091209.pdf
Files
Additional details
- Eprint ID
- 46640
- Resolver ID
- CaltechAUTHORS:20140702-132433985
- AAUW Dissertation Fellowship
- Tertiary Education Commission Top Achiever Doctoral scholarship
- ATM-0432377
- NSF
- CHE-0211496
- NSF
- Royal Society of New Zealand Marsden Fund
- Created
-
2014-07-02Created from EPrint's datestamp field
- Updated
-
2021-11-10Created from EPrint's last_modified field
- Caltech groups
- Division of Geological and Planetary Sciences