Ultrafast ring opening in CHD investigated by simplex-based spectral unmixing

Details Ultrafast ring opening in CHD investigated by simplex-based spectral unmixing Ultrafast ring opening in CHD investigated by simplex-based spectral unmixing

2011-09-13

arxiv.org/abs/1109.2702v1

Physics

Chemical Physics

Scientific paper

We use spectral unmixing to determine the number of transient photoproducts and to track their evolution following the photo- excitation of 1,3-cyclohexadiene (CHD) to form 1,3,5-hexatriene (HT) in the gas phase. The ring opening is initiated with a 266 nm ultraviolet laser pulse and probed via fragmentation with a delayed intense infrared 800 nm laser pulse. The ion time-of-flight (TOF) spectra are analyzed with a simplex-based spectral unmixing technique. We find that at least three independent spectra are needed to model the transient TOF spectra. Guided by mathematical and physical constraints, we decompose the transient TOF spectra into three spectra associated with the presence of CHD, CHD+, and HT, and show how these three products appear at different times during the ring opening.

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