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OH-Stretch Vibrational Spectroscopy of Hydroxymethyl Hydroperoxide

Fry, Juliane L. and Matthews, Jamie and Lane, Joseph R. and Roehl, Coleen M. and Sinha, Amitabha and Kjaergaard, Henrik G. and Wennberg, P. O. (2006) OH-Stretch Vibrational Spectroscopy of Hydroxymethyl Hydroperoxide. Journal of Physical Chemistry A, 110 (22). pp. 1072-7079. ISSN 1089-5639. doi:10.1021/jp0612127.

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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.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Roehl, Coleen M.0000-0001-5383-8462
Sinha, Amitabha0000-0002-7122-3549
Kjaergaard, Henrik G.0000-0002-7275-8297
Wennberg, P. O.0000-0002-6126-3854
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.
Group:UNSPECIFIED, Division of Geological and Planetary Sciences
Funding AgencyGrant Number
AAUW Dissertation FellowshipUNSPECIFIED
Tertiary Education Commission Top Achiever Doctoral scholarshipUNSPECIFIED
Royal Society of New Zealand Marsden FundUNSPECIFIED
Issue or Number:22
Record Number:CaltechAUTHORS:20140702-132433985
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Official Citation:OH-Stretch Vibrational Spectroscopy of Hydroxymethyl Hydroperoxide Juliane L. Fry, Jamie Matthews, Joseph R. Lane, Coleen M. Roehl, Amitabha Sinha, Henrik G. Kjaergaard, and, and Paul O. Wennberg, The Journal of Physical Chemistry A 2006 110 (22), 7072-7079
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:46640
Deposited By: Ruth Sustaita
Deposited On:02 Jul 2014 21:22
Last Modified:10 Nov 2021 17:28

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