Landscapes of Four-Enantiomer Conical Intersections for Photoisomerization of Stilbene: CASSCF Calculation

Abstract

The photoisomerization of cis- and trans-stilbene through conical intersections (CI) is mainly governed by four dihedral angles around central C=C double bonds. The two of them are C-C=C-C and H-C=C-H dihedral angles that are found to form a mirror rotation coordinate, and the mirror plane appears at the two dihedral angles equal to zeros with which the middle state is defined through partial optimization. There exist the first-type of hula-twist-CI enantiomers, the second-type of hula-twist-CI enantiomers, the first-type of one-bond-flip-CI enantiomers, and the second type of one-bond-flip-CI enantiomers as well as cis-enantiomers and trans-enantiomers with respect to this mirror plane. The complete active space self-consistent field method is employed to calculate minimum potential energy profile along the mirror rotation coordinate for each enantiomers, and it is found that the left-hand manifold and the right-hand manifold of potential energy surfaces can be energetically transferred via photoisomerization. Furthermore, two-dimensional potential energy surfaces in terms of the branching plane g-h coordinates are constructed at vicinity of each conical intersection, and the landscapes of conical intersections show distinct feature, and in excited-state four potential wells separated in different section of g-h plane related to different conical intersections which indicate different photoisomerization pathways.