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Rules of Two-Photon Concerted Photochemical Pericyclic Reactions and Its Difference from Woodward-Hoffman Rules for One-Photon Cases
ZHANG Xian-Fu *
Hebei Normal University of Science and Technology
*Correspondence author
#Submitted by
Subject:
Funding:
none
Opened online:26 March 2013
Accepted by:
none
Citation: ZHANG Xian-Fu.Rules of Two-Photon Concerted Photochemical Pericyclic Reactions and Its Difference from Woodward-Hoffman Rules for One-Photon Cases[OL]. [26 March 2013] http://en.paper.edu.cn/en_releasepaper/content/4528316
A two-photon (with frequency v) reaction (TPR) is compared with its corresponding one-photon (with frequency 2v) counterpart (OPR) both experimentally and theoretically. TPR often yields different products from its OPR, suggesting Woodward-Hoffman Rules do not apply for TPR. To explain the difference, it is proposed that Hudson-Kohler state of polyenes (HKSP), rather than the state in Huckel molecular orbital theory, acts as the lowest-lying excited state for the two-photon absorption (TPA) involved in TPR. The selection rules for pericyclic TPR are derived based on the symmetry of HKSP and frontier orbital theory.