Time-resolved dissociative intense-laser field ionization for probing dynamics: Femtosecond photochemical ring opening of 1,3-cyclohexadiene

Publisher Website
Google Scholar
Abstract
The concerted photochemical ring opening of 1,3-cyclohexadiene was investigated in the gas phase by low-intensity pumping at 267 nm and subsequent probing by high-intensity photoionization at 800 nm and mass-selective detection of the ion yields. We found five different time constants which can be assigned to traveling times along consecutive parts of the potential energy surfaces. The molecule is first accelerated in the spectroscopic state 1B along Franck–Condon active coordinates, then alters direction before changing over to the dark state 2A. All constants including that for leaving the 2A surface are below 100 fs. These times are shorter than appropriate vibrational periods. Such a maximum speed is evidence that the pathway is continuous leading from surface to surface via real crossings (conical intersections) and that the molecule is accelerated right into the outlet of the 2A/1A funnel. On the ground state it arrives as a compact wave packet, indicating a certain degree of coherence. The experimental method promises a high potential for investigating dynamics, since many consecutive phases of the process can be detected. This is because the fragmentation pattern depends on the location on the potential energy surface, so that monitoring several different ions permits to conclude on the population flow through these locations. Ionization at the intensities used is normally considered to be an effect of the electric field of the radiation. But in our case it is enhanced by resonances in the neutral molecule and in particular in the singly positive ion, and it is not sensitive for the length of the molecule (different conformers of the product hexatriene). The ionic resonances explain why hexatriene has a much richer fragmentation pattern than cyclohexadiene. Coulomb explosion is observed from an excited state of a doubly positive ion. Its mechanism is discussed.