Non-vertical Excitation Energies for Low-lying Singlet States of Butadiene and Hexatriene
Results are presented from ab initio CI calculations for three low-lying singlet states of all-trans-butadiene and -hexatriene. Using estimates of relaxed (planar) excited-state geometries we have calculated 0-0 excitation energies for the 1 1Bu and 2 1Ag states for each molecule. We obtain good agreement with experimental 0-0 transition energies for the 1 1Bu, states. For both molecules the 1 1Bu, and 2 1Ag 0-0 transition energies are found to be essentially equal. The energies of the 2 1Ag states are shown to be highly sensitive to geometric variations.
© 1988 Published by Elsevier B.V.
Robert J. Cave, Ernest R. Davidson, Non-vertical excitation energies for low-lying singlet states of butadiene and hexatriene, Chemical Physics Letters, Volume 148, Issues 2–3, 8 July 1988, Pages 190-196, ISSN 0009-2614, http://dx.doi.org/10.1016/0009-2614(88)80297-5. (http://www.sciencedirect.com/science/article/pii/0009261488802975)