A Preliminary Study of Host-Guest Interactions in Polymeric Clathrates – An Ab Initio Study of the Model Complexes Benzene/X2 (X = F, Cl, Br, I)

A systematic ab initio investigation of the complexes benzene/halogen molecules is presented. For the whole halogen series, the T-shaped geometry is clearly favored relative to the sandwich geometry. This preference is rationalized in terms of the electrostatic fields generated by the interacting molcules. Higher binding energies have been calculated on going from /F2 to /I2 molecular complexes.