− Absorption of Propargyl Peroxy Radical (H−C≡C−CH2OO·): A Cavity Ring-Down Spectroscopic and Computational Study
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- 作者：Phillip S. Thomas ; Neal D. Kline ; Terry A. Miller
- 刊名：Journal of Physical Chemistry A
- 出版年：2010
- 出版时间：December 2, 2010
- 年：2010
- 卷：114
- 期：47
- 页码：12437-12446
- 全文大小：361K
- 年卷期：v.114,no.47(December 2, 2010)
- ISSN：1520-5215
文摘
The − electronic absorption spectrum of propargyl peroxy radical has been recorded at room temperature by cavity ring-down spectroscopy. Electronic structure calculations predict two isomeric forms, acetylenic and allenic, with two stable conformers for each. The acetylenic trans conformer, with a band origin at 7631.8 ± 0.1 cm−1, is definitively assigned on the basis of ab initio calculations and rotational simulations, and possible assignments for the acetylenic gauche and allenic trans forms are given. A fourth form, allenic cis, is not observed. Simulations based on calculated torsional potentials predict that the allenic trans form will have a long, poorly resolved progression in the OOCC torsional vibration, consistent with experimental observations.