An ab initio study of the excited states, isomerization energy profiles and conical intersections of a chiral cyclohexylidene derivative

作者：Schreiber Marko; Barbatti Mario^*; Zilberg Shmuel; Lischka Hans; Gonzalez Leticia

来源：Journal of Physical Chemistry A, 2007, 111(2): 238-243.

DOI：10.1021/jp066090x

The excited valence and Rydberg states of the chiral (4-methylcyclohexylidene) fluoromethane (4MCF) have been investigated using multiconfigurational CASSCF and CASPT2, and coupled-cluster methods (RI-CC2). A 3s Rydberg state is predicted below the valence (1)pi pi* state. To gain insight into the photophysics of the cis-trans isomerization of this olefin, potential energy profiles for the valence (1)pi pi* state along the twisting and pyramidalization reaction coordinates have been computed using variational methods (CASSCF and multireference configuration interaction with singles and doubles (MR-CISD)). Starting from geometries with energies close to degeneracy in the valence and ground-state curves, three minima on the crossing seam that can be correlated with the conical intersections known for fluoroethylene, have been found. On the basis of these features, the photochemistry of 4MCF is discussed.

• 出版日期2007-1-18