Transition states and nonlinear excitations in chloroform observed with a sub-5 fs pulse laser

Izumi Iwakura, Atsushi Yabushita, Takayoshi Kobayashi*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

20 Scopus citations


Sub-5 fs pulse dynamics observed in neat chloroform (CHCl3) and the CHCl3 ⋯ O2 charge-transfer complex in oxygen-saturated chloroform (O2-CHCl3) were found to be dominated by wave packet motions in the excited state and the ground state, respectively. The time-resolved signal of CHCl3 exhibits dynamics in the electronic excited state generated by a three-photon absorption process, and that of O2-CHCl3 is explained in terms of the dynamics of the electronic ground state excited by the stimulated Raman process. In addition, we found that the oxidation reaction of chloroform in the charge-transfer complex of chloroform and oxygen easily proceeds via a C-H insertion process triggered by the stimulated Raman process under the irradiation of a visible laser pulse. The spectrogram analysis enabled direct observation of the realtime dynamics of the Raman-triggered oxidation process. These results demonstrate that observation of transition states by sub-5 fs time-resolved spectroscopy is applicable to "ground-state reactions" as well as "excited-state reactions" via stimulated Raman excitation in a wide variety of chemical reactions.

Original languageEnglish
Pages (from-to)688-696
Number of pages9
JournalJournal of the American Chemical Society
Issue number2
StatePublished - 21 Jan 2009

Fingerprint Dive into the research topics of 'Transition states and nonlinear excitations in chloroform observed with a sub-5 fs pulse laser'. Together they form a unique fingerprint.

Cite this