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.
Highlights
Electrocyclic reactions play important roles in biological activities[1] and in photoelectric functions.[2]
We investigated the ring-opening dynamics pumped by two photons of 400 nm (1⁄43.1 eV) light and probed it by Time-resolved photoelectron spectroscopy (TRPES) using high harmonic pulses with a photon energy of 29.5 eV
It is worth mentioning that the molecular orbitals (MOs) with À12.56, À13.19, and À14.11 eV have a high density at the C5–C6 bond that cleaves upon photoexcitation
Summary
Electrocyclic reactions play important roles in biological activities[1] and in photoelectric functions.[2]. We investigated the ring-opening dynamics pumped by two photons of 400 nm (1⁄43.1 eV) light and probed it by TRPES using high harmonic pulses with a photon energy of 29.5 eV.
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