The positive and neutral clusters produced by the impact of similar to 60 MeV Cf-252 fission fragments on a LiF polycrystalline target are analyzed. The positive ion spectrum is dominated by the (LiF)(n)Li+ series, n = 0-7, exhibiting a total yield 2 orders of magnitude higher than that of the (LiF)(n)(+) series. The yield for the dominant (LiF)(n)Li+ series decreases roughly as exp(-kn), where k approximate to 0.9 for n = 0-3 and k approximate to 0.6 for the heavier clusters (n = 4-9), while the yield of the (LiF)(n)(+) series also decreases exponentially as n increases with k approximate to 0.6. Theoretical calculations were performed for the (LiF)(n)Li-0, (LiF)(n)Li+, and (LiF)(n)(0) series for n up to 9. For the smaller clusters the structures first obtained with a genetic algorithm generator were further optimized at the DFT/B3LYP/6-311+G(3df), DFT/B3LYP/LACV3P*, and MP2/LACV3P* levels of theory. An energy criterion is used for a proper taxonomic description of the optimized cluster isomers. Cluster properties such as fragmentation energy and stability are discussed for the proposed configurations. The results show that for all three series the most stable isomers present a linear structure for small cluster size (n = 1-3), while cubic cells or polyhedral structures are preferred for larger cluster sizes (n = 4-9). Fragmentation energy results suggest that a desorbed excited (LiF)(n)Li+ ion preferentially dissociates via a cascade of (LiF)(n)(0) units, in agreement with the slope modification in the exponential decay of the (LiF)(n)Li+ ion abundances for n >= 3.