involved in the first steps in the photochemistry initiated by ultraviolet (266-nm wavelength) excitation of solutions of 1,5-hexadiene, isoprene, and 2,3-dimethylbut-2-ene in carbon tetrachloride or chloroform. Ultraviolet and visible bands centered close to 330 and 500 nm in both solvents are assigned respectively to a charge transfer band of Cl-solvent complexes and the strong absorption band of a higher energy isomeric form of the solvent molecules (iso-CCl3-Cl or iso-CHCl2-Cl). These assignments are supported by calculations of electronic excitation energies. The isomeric forms have significant contributions to their structures from charge-separated resonance forms and offer a reinterpretation of previous assignments of the carriers of the visible bands that were based on pulsed radiolysis experiments. Kinetic analysis demonstrates that the isomeric forms are produced via the Cl solvent complexes. Addition of the unsaturated hydrocarbons provides a reactive loss channel for the Cl solvent complexes, and reaction radii and bimolecular rate coefficients are derived from analysis using a Smoluchowski theory model. For reactions of Cl with 1,5-hexadiene, isoprene, and 2,34imethylbut-2-ene in CCl4, rate coefficients at 294 K are, respectively, (8.6 +/- 0.8) X 109, (9.5 +/- 1.6) X 109, and (1.7 +/- 0.1) x 1010 The larger reaction radius and rate coefficient for 2,3dimethylbut-2-ene are interpreted as evidence for an H-atom abstraction channel that competes effectively with the channel involving addition of a Cl-atom to a C = C bond. However, the addition mechanism appears to dominate the reactions of 1,5-hexadiene and isoprene. Two-photon excited CCl4 or CHCl3 can also ionize the diene or alkene solute.