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Volume 194, 2016
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Structural dynamics of photochemical reactions probed by time-resolved photoelectron spectroscopy using high harmonic pulses

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Abstract

Femtosecond ring-opening dynamics of 1,3-cyclohexadiene (CHD) in gas phase upon two-photon excitation at 400 nm (=3.1 eV) was investigated by time-resolved photoelectron spectroscopy using 42 nm (=29.5 eV) high harmonic photons probing the dynamics of the lower-lying occupied molecular orbitals (MOs), which are the fingerprints of the molecular structure. After 500 fs, the photoelectron intensity of the MO constituting the C[double bond, length as m-dash]C sigma bond (σC[double bond, length as m-dash]C) of CHD was enhanced, while that of the MO forming the C–C sigma bond (σCC) of CHD was decreased. The changes in the photoelectron spectra suggest that the ring of CHD opens to form a 1,3,5-hexatriene (HT) after 500 fs. The dynamics of the σC[double bond, length as m-dash]C and σCC bands between 200 and 500 fs reflects the ring deformation to a conical intersection between the 21A and 11A potential energy surfaces prior to the ring-opening reaction.

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Publication details

The article was received on 31 Mar 2016, accepted on 31 May 2016, published on 31 May 2016 and first published online on 31 May 2016


Article type: Paper
DOI: 10.1039/C6FD00063K
Citation: Faraday Discuss., 2016,194, 147-160
  • Open access: Creative Commons BY license
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    Structural dynamics of photochemical reactions probed by time-resolved photoelectron spectroscopy using high harmonic pulses

    R. Iikubo, T. Sekikawa, Y. Harabuchi and T. Taketsugu, Faraday Discuss., 2016, 194, 147
    DOI: 10.1039/C6FD00063K

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