Vibronic interactions in charged chlorocubane, (CCl)8

Electron-phonon interactions in charged chlorocubane ((CCl)8) are studied. The estimated total electron-phonon coupling constants for the monoanion (lLUMO) and cation (lHOMO) of chlorocubane are 1.018 and 0.276 eV, respectively. The lLUMO value for chlorocubane is larger than that for fluorocubane ((CF)8). The higher electron density on chlorine atoms in the LUMO in (CCl)8 than that on fluorine atoms in (CF)8, and the large displacements of chlorine and fluorine atoms in (CCl)8 and (CF)8, respectively, are the main reason for the calculational results. The lHOMO value for (CCl)8 is much smaller than that for (CF)8. Weaker orbital interactions between carbon and chlorine atoms in the HOMO in (CCl)8 than those between carbon and fluorine atoms in the HOMO in (CF)8, is the main reason for the calculational results. The single charge transfer through (CF)8 and (CCl)8 is also discussed.