The potential energy paths (i.e., the minimum energy paths) that control the excited-state evolution of cyclohexadiene (CHD) and cZc-hexatriene (cZc-HT) from the Franck-Condon (FC) region are documented. These paths indicate that both CHD and cZc-HT undergo a barrierless motion in the IB? spectroscopic State until decay to the lower lying (2)A(1) state occurs via two distinct B-1(2)/(2)A(1) conical intersections. Remarkably, it is found that both conical intersections correspond to open (i.e., acyclic) molecular structures. On the basis of these results and of the available experimental data, it is concluded that although the photochemical ring-opening of CHD occurs (in femtoseconds) in the spectroscopic state, the associated photochemical ring closure reaction of cZc-HT is initiated upon decay of (2)A(1) cZc-HT to the ground state picoseconds after the initial excitation.