Please use this identifier to cite or link to this item: http://hdl.handle.net/10397/14588
Title: Observation of singlet cycloreversion of thymine oxetanes by direct photolysis
Authors: Kwok, WM 
Guan, X
Chu, LM
Tang, W
Phillips, DL
Issue Date: 2008
Publisher: American Chemical Society
Source: Journal of physical chemistry B, 2008, v. 112, no. 37, p. 11794-11797 How to cite?
Journal: Journal of physical chemistry B 
Abstract: An ultrafast broadband transient absorption spectroscopic study of the direct photolysis of oxetane DMT-BP [which is the oxetane adduct of 1,3-dimethylthymine (DMT) with benzophenone (BP)] is presented. Previous nanosecond time-resolved absorption studies by other researchers observed that direct photolysis of such oxetanes results in a rare, adiabatic photochemical reaction to produce a triplet excited-state carbonyl species. However, the mechanism for this adiabatic photochemical reaction remained unclear for the reaction sequence of the bond scission and the intersystem crossing (ISC) because of the time resolution for the experiments, and this prompted us to further study its mechanism with ultrafast time-resolution. The ultrafast time-resolved spectra presented here indicate that the cycloreversion reaction occurs in a stepwise manner on a singlet excited-state, and then intersystem crossing (ISC) occurs to produce the triplet carbonyl product observed in the previously reported nanosecond time-resolved experiments.
URI: http://hdl.handle.net/10397/14588
ISSN: 1520-6106
EISSN: 1520-5207
DOI: 10.1021/jp803099s
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