The ground-state properties of the doped alkali-metal cluster, Li9F, have been investigated using extended basis Hartree-Fock calculations. Six isomers were found. The excited states of the isomers were modeled via configuration-interaction singles (CIS). Differences between the optical response of the isomers with an external fluorine and with an internal fluorine were found. Comparisons are also made between the CIS results for the isomers of Li9F and the homogeneous clusters, Li-8 and Li-9(+). The ground-state studies show that the metallic Li-8 core is resistant to substantial modification; the added LiF modifies the geometry and the symmetry in all six isomers, but the frontier molecular orbital structure is only slightly changed from the parent Li-8 cluster. All six isomers found are substantially noncentrosymmetric. The reduced symmetry permits optical absorption at many more frequencies than can be seen in the more highly symmetric Li-8 or Li-9(+) parents, but the overall spectral pattern is very similar.