Results from ab initio calculations concerning several low-lying electronic states of trans,trans-1,3,5-hexatriene are presented and compared with experimental and previous theoretical results. The lowest excited singlet state is predicted to be the ¹B_u state, having essentially valencelike π → π* character. The nominally doubly excited 2¹A_g state is found to lie approximately 0.6-0.9 eV above the 1¹B_u state. Results are also presented for several Rydberg states. The implications of the present results for current parametrizations of semiempirical π molecular orbital schemes are discussed.
© 1988 American Chemical Society
Cave, R.J.; Davidson, E.R. “A Theoretical Investigation of Several Low-Lying States of trans, trans 1,3,5-Hexatriene,'' J. Phys. Chem. 1988, 92, 614. doi: 10.1021/j100314a009