Photodissociation of tert-butyl hypochlorite and decomposition of the tert-butoxy radical fragment
Thelen, M.A., Felder, P., Frey, J.G. and Huber, J.R. (1993) Photodissociation of tert-butyl hypochlorite and decomposition of the tert-butoxy radical fragment. Journal of Physical Chemistry, 97, (23), 6220-6225.
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Description/Abstract
The photochemistry of tert-butyl hypochlorite (TBOCl) has been studied in a molecular beam by photofragment translational spectroscopy. After laser excitation at 248 or 308 nm, the TBOCI molecule decays exclusively into a tert-butoxy radical (TBO) and a Cl atom. The photolysis at 248 nm releases almost- equal-to 60% of the available energy into the photofragment recoil which is highly anisotropic (beta = 1.9 +/- 0. 1), implying a direct dissociation mechanism and an electronic transition dipole moment mu over arrow pointing right in the parent molecule that is oriented along the O-Cl bond. Approximately 90% of the nascent TBO radicals formed at 248 nm have sufficient internal energy to undergo a secondary decay into methyl radicals and acetone, while at 308 nm TBO is stable. From a comparison of the time-of-flight distributions of the primary fragments Cl and TBO and on the basis of the dissociation energy D0(1)(TBO - Cl) = 50 kcal/mol of the primary reaction, the threshold energy for the unimolecular decay of TBO is found to be E0 = 20 +/- 3 kcal/mol, a value which is higher than the previously reported gas kinetic activation energy E(a) = 15 kcal/mol.
| Item Type: | Article |
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| Related URLs: | |
| Subjects: | Q Science > QD Chemistry |
| Divisions: | University Structure - Pre August 2011 > School of Chemistry |
| Item ID: | 15928 |
| Date Deposited: | 17 Jun 2005 |
| Last Modified: | 01 Jun 2011 01:41 |
| Contributors: | Thelen, M.A. (Author) Felder, P. (Author) Frey, J.G. (Author) Huber, J.R. (Author) |
| Date: | 1993 |
| Status: | Published |
| URI: | http://eprints.soton.ac.uk/id/eprint/15928 |
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