Competition Between Concerted and Stepwise Dynamics in the Triplet Di-π-Methane Rearrangement†
Dr. Gonzalo Jiménez-Osés
Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095-1569 (USA)
Search for more papers by this authorDr. Peng Liu
Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095-1569 (USA)
Search for more papers by this authorDr. Ricardo A. Matute
Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095-1569 (USA)
Search for more papers by this authorCorresponding Author
Prof. Dr. Kendall N. Houk
Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095-1569 (USA)
Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095-1569 (USA)Search for more papers by this authorDr. Gonzalo Jiménez-Osés
Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095-1569 (USA)
Search for more papers by this authorDr. Peng Liu
Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095-1569 (USA)
Search for more papers by this authorDr. Ricardo A. Matute
Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095-1569 (USA)
Search for more papers by this authorCorresponding Author
Prof. Dr. Kendall N. Houk
Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095-1569 (USA)
Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095-1569 (USA)Search for more papers by this authorThis research was supported by the National Science Foundation (CHE-1059084). Calculations were performed on the Hoffman2 and Dawson2 GPU clusters at UCLA and the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the National Science Foundation (OCI-1053575).
Abstract
The molecular dynamics of the triplet-state Zimmerman di-π-methane rearrangement of dibenzobarrelene were computed with B3LYP and M06-2X density functionals. All productive quasiclassical trajectories involve sequential formation and cleavage of CC bonds and an intermediate with lifetimes ranging from 13 to 1160 fs. Both dynamically concerted and stepwise trajectories are found. The average lifetime of this intermediate is significantly shorter than predicted by either transition-state theory or the Rice–Ramsperger–Kassel–Marcus model, thus indicating the non-statistical nature of the reaction mechanism.
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