A new reaction mechanism of Claisen rearrangement induced by few-optical-cycle pulses: Demonstration of nonthermal chemistry by femtosecond vibrational spectroscopy

Izumi Iwakura*, Atsushi Yabushita, Jun Liu, Kotaro Okamura, Satoko Kezuka, Takayoshi Kobayashi

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

Time-resolved vibration spectroscopy is the only known way to directly observe reaction processes. In this work, we measure time-resolved vibration spectra of the Claisen rearrangement triggered and observed by few-optical-cycle pulses. Changes in molecular structure during the reaction, including its transition states (TSs), are elucidated by observing the transient changes of molecular vibration wavenumbers. We pump samples with visible ultrashort pulses of shorter duration than the molecular vibration period, and with photon energies much lower than the minimum excitation energy of the sample. The results indicate that the "nonthermal Claisen rearrangement" can be triggered by visible few-optical-cycle pulses exciting molecular vibrations in the electronic ground state of the sample, which replaces the typical thermal Claisen rearrangement.

Original languageEnglish
Pages (from-to)1991-2004
Number of pages14
JournalPure and Applied Chemistry
Volume85
Issue number10
DOIs
StatePublished - Oct 2013

Keywords

  • Laser spectroscopy
  • Reaction mechanisms
  • Rearrangements

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