Intramolecular Electron Transfer in Nonconjugated Polyenes

The probability of hole-propagation of initially prepared vacancies in 1,5-hexadiene (1) and 1,6-heptadiene (2) as well as the transfer mechanisms in 1 and 2 are studied by means of timedependent perturbation theory. Times of equibrilation of about 10-15 sec are calculated. Local perturbations in the π moieties are efficiently transmitted via CH-σ states while CC-σ functions and the direct transfer channel are less important. The theoretical key step consist in an unitary transformation of the canonical molecular orbitals (CMO's) with the diagonal Fock operator into a set of one-electron states forming a transport-type Fockian, FHT, where only a few matrix elements (between the evoluting orbitals and a set of messenger states) differ from zero.