Using ab initio and density functional calculations, we studied photoexcitation of a charge-balanced electron donor–acceptor (DA) complex comprised of tetracyanoethylene (TCE) and tetramethylethylene (TME). We considered both the TCE-TME stacked conformer and a possible conformer with a solvent molecule (dichloromethane) inserted between TCE and TME. The photoexcitation of the DA complex can directly form a charge transfer (CT) state. Our theoretical investigations show that the CT state can also be produced from the decay of higher excited states. Using the continuum model, we investigated the solvent effects on CT absorption, local excitation, and CT emission in the polar solvent. The equilibrium solvation energies of the ground and excited states of the DA complex were calculated using the self-consistent reaction field method, and then the correction of nonequilibrium solvation energies for the vertical transitions was made. The transition energies (i.e., CT absorption for the DA complexes and CT emission for the contact ion pair complexes) in the polar solvent show redshifts relative to those in the gas phase. © 2003 American Institute of Physics.