  We extend Mulliken's theory of ground state charge transfer in a
donor-acceptor complex to excited state charge transfer between pairs of
identical $\pi$-conjugated oligomers, one of which is in the optically excited
state and the other in the ground state, leading to the formation of a
charge-transfer exciton. Within our theory, optical absorptions from the
charge-transfer exciton should include a low energy intermolecular
charge-transfer excitation, as well as distinct intramolecular excitations from
both the neutral delocalized exciton component and the Coulombically bound
polaron-pair component of the charge-transfer exciton. We report high order
configuration-interaction calculations for pairs of oligomers of
poly-paraphenylenevinylene (PPV) that go beyond our previous single
configuration-interaction calculation and find all five excited state
absorptions predicted using heuristic arguments based on the Mulliken concept.
Our calculated excited state absorption spectrum exhibits strong qualitative
agreement with the complete wavelength-dependent ultrafast photoinduced
absorption in films of PPV derivatives, suggesting that a significant fraction
of the photoinduced absorption here is from the charge-transfer exciton. We
make detailed comparisons to experiments, and a testable experimental
prediction.
