Direct absorption spectroscopy of jet-cooled polyenes. I. The 1 1B+u←1 1Ag transition of t r a n s, t r a n s-1,3,5,7-octatetraene

Abstract
The direct absorption spectrum of the 1 1B+u←1 1Ag transition of jet‐cooled trans,trans‐1,3,5,7‐octatetraene is reported here for the 35, 120–42, 600 cm1 region. The alleviation of vibrational sequence band congestion in the jet spectrum results in an order‐of‐magnitude decrease in the observed breadth of the origin band and a comparable sharpening throughout the spectrum, enabling the redetermination of vibronic band positions, relative intensities, and widths. Vibrational assignments for the seven observed active modes are discussed, and results are compared to the predictions of previously reported vibronic structure calculations.

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