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Updated: Jun 7, 2026

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
Published on: August 6, 2018
Ã-X absorption of propargyl peroxy radical (H-C≡C-CH2OO·): a cavity ring-down spectroscopic and computational study
Phillip S Thomas1, Neal D Kline, Terry A Miller
1Department of Chemistry, The Ohio State University, 120 West 18th Avenue, Columbus, Ohio 43210, USA.
Abstract:
The Ã-X 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.
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