Structural dynamics of photochemical reactions probed by time-resolved photoelectron spectroscopy using high harmonic pulses
Open Access
- 31 May 2016
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Faraday Discussions
- Vol. 194, 147-160
- https://doi.org/10.1039/c6fd00063k
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 CC sigma bond (σCC) 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 σCC 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.Keywords
Funding Information
- Japan Society for the Promotion of Science (15H03702, 16K13854, 26288001, 26600107)
- Core Research for Evolutional Science and Technology, Japan Science and Technology Agency
This publication has 43 references indexed in Scilit:
- Ultrafast ring opening in 1,3-cyclohexadiene investigated by simplex-based spectral unmixingThe Journal of Chemical Physics, 2012
- Electronic structure in real time: mapping valence electron rearrangements during chemical reactionsPhysical Chemistry Chemical Physics, 2011
- The Ultrafast Pathway of Photon-Induced Electrocyclic Ring-Opening Reactions: The Case of 1,3-CyclohexadieneAnnual Review of Physical Chemistry, 2011
- Real-Time Evolution of the Valence Electronic Structure in a Dissociating MoleculePhysical Review Letters, 2009
- Ab initio nonadiabatic quantum dynamics of cyclohexadiene/hexatriene ultrafast photoisomerizationThe Journal of Chemical Physics, 2006
- Measurement of the Intensity-Dependent Atomic Dipole Phase of a High Harmonic by Frequency-Resolved Optical GatingPhysical Review Letters, 2002
- Electronic Spectra of 1,4-Cyclohexadiene and 1,3-Cyclohexadiene: A Combined Experimental and Theoretical InvestigationThe Journal of Physical Chemistry A, 1999
- Solvent effect on previtamin D conformational equilibrium and photoreactionsJournal of Photochemistry and Photobiology A: Chemistry, 1997
- Observation of Laser Assisted Photoelectric Effect and Femtosecond High Order Harmonic RadiationPhysical Review Letters, 1996
- Improved photosynthesis of previtamin D by wavelengths of 280–300 nmJournal of Photochemistry and Photobiology A: Chemistry, 1991