Faculty Publications

Spectroscopic and Thermochemical Consequences of Site-Specific H-Atom Addition to Naphthalene

Document Type

Article

Journal/Book/Conference Title

Journal of Physical Chemistry A

Volume

114

Issue

21

First Page

6255

Last Page

6262

Abstract

Vibronic spectra of doublet-doublet transitions of 1-hydronaphthyl (1HN), 2-hydronaphthyl (2HN), and 1,2,3-trihydronaphthyl (THN, tetralyl) radicals have been recorded under jet-cooled conditions. Transitions due to the two C 10H9 isomers were identified and assigned based on the choice of radical precursor, visible-visible hole-burning spectroscopy, comparison of observed vibronic transitions with calculation, and photoionization efficiency scans. The latter provided accurate ionization potentials for the three free radicals (IP(1HN) = 6.570 eV, IP(2HN) = 6.487 eV, IP(THN) = 6.620 eV, errors ±0.002 eV). A thermochemical cycle is used to extract from these ionization potentials the C-H bond dissociation energy (BDE) of 1HN at the 1-position of 121.2 ± 2 kJ/mol. Using proton affinities of 2HN and THN calculated at the G3(MP2, CC)//B3LYP/6-311G* level of theory, the corresponding C-H BDEs of 2HN at the 2-carbon (103.6 ± 2 kJ/mol) and of THN at the 3-position (168 ± 3 kJ/mol) are derived. The possible role played by these hydronaphthyl radicals in Titans atmosphere, the interstellar medium, and combustion are briefly discussed. © 2010 American Chemical Society.

Department

Department of Chemistry and Biochemistry

Original Publication Date

6-3-2010

DOI of published version

10.1021/jp103793e

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