Theoretical study on hula-twist motion of penta-2,4-dieniminium on the S1 surface under isolated condition by the complete active space self-consistent field theory

Hula-twist (HT) motion of tZt-penta-2,4-dieniminium (PDI) on the S1 surface is studied on the basis of complete active space self-consistent field (CASSCF) theory. An S1/S0 crossing region (a segment of the S1/S0 conical intersection hyperline) along a HT coordinate (simultaneous rotation of the central double bond and an adjacent single bond) is characterized. One-dimensional relaxed scan calculation along the postulated HT coordinate shows no barrier up to the S1/S0 crossing region, suggesting the possible involvement of the HT process in a fast photochemical reaction in constrained states.

Graphical abstractA S1/S0 degeneracy space (hyperline) of the title compound was studied along the so-called Hula-twist (HT) coordinate [simultaneous rotations of double bond (θ) and its neighboring single bond (ϕ)]. This S1/S0 hyperline lies well below the Franck-Condon region, suggesting a possible involvement of the HT motion in photoreactions.Download full-size image