Competing ultrafast cis-trans isomerization and ring closure of cyclohepta-1,3-diene and cyclo-octa-1,3-diene

Authors: Fuß, W.; Panja, S.; Schmid, W. E.; Trushin, S. A.

Source: Molecular Physics, Volume 104, Numbers 5-7, -7/10 March-10 April 2006 , pp. 1133-1143(11)

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Abstract:

Photochemically, s-cis -dienes can undergo cis-trans isomerization or electrocyclic ring closure to cyclobutenes. Modern quantum chemistry predicts that both reactions can originate from the same conical intersection and explains thereby why photochemical ring opening of cyclobutenes to dienes is often not stereospecific, although ring closure of dienes is. Evidence is found that the reaction path already branches earlier, investigating two cyclic dienes which were excited by a femtosecond UV pulse in the gas phase and probed by photoionization at 810nm. The multistep path is assigned to the excited-state surfaces and ring closure of the ground-state trans isomers is also detected.

Document Type: Research article

DOI: http://dx.doi.org/10.1080/00268970500417408

Affiliations: 1: Max-Planck-Institut für Quantenoptik, Germany

Publication date: 2006-01-01

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