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Photoisomerization of the linear polyene 1,3,5,7-octatetraene has been observed in an n-hexane matrix maintained at the boiling point of helium. To a good approximation, only the trans,trans and cis,trans isomers participate in the photochemistry. These compounds have been unambiguously identified by comparing the observed high-resolution fluorescence spectra to those of chromatographically purified reference compounds. Although the quantum yield of this process is probably low, its microscopic rate seems to compete favorably with vibrational deactivation.

cis-trans photoisomerization of 1,3,5,7-octatetraene in n -hexane at 4.2 K