Spectroscopy and femtosecond dynamics of the ring opening reaction of 1,3-cyclohexadiene
Journal Article
·
· Journal of Chemical Physics
- Department of Physics and Astronomy, College of Charleston, Charleston, South Carolina 29424 (United States)
The early stages of the ring opening reaction of 1,3-cyclohexadiene to form its isomer 1,3,5-hexatriene, upon excitation to the ultrashort-lived 1 {sup 1}B{sub 2} state, were explored. A series of one-color two-photon ionization/photoelectron spectra reveal a prominent vibrational progression with a frequency of 1350 cm{sup -1}, which is interpreted in a dynamical picture as resulting from the ultrafast wave packet dynamics associated with the ring opening reaction. Photoionization in two-color three-photon and one-color four-photon ionization schemes show an ionization pathway via the same ultrashort-lived 1 {sup 1}B{sub 2} state, and in addition, a series of Rydberg states with quantum defects of 0.93, 0.76, and 0.15, respectively. Using those Rydberg states as probes for the reaction dynamics in a time-resolved pump-probe experiment provides a direct observation of the elusive 2 {sup 1}A{sub 1} state that has been implicated as an intermediate step between the initially excited 1 {sup 1}B{sub 2} state and the ground electronic state. The rise and decay times for the 2 {sup 1}A{sub 1} state were found to be 55 and 84 fs, respectively.
- OSTI ID:
- 20864303
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 13 Vol. 125; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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