Charles D. Cowman

Electronic structure of Re2Cl82

Abstract The multiple scattering Xα method has been used to calculate the ordering of both occupied and unoccupied one-electron energy states of Re 3 Cl 8 2− . Single crystal polarized electronic spectra of [( n -C 4 H 9 ) 4 N] 2 [Re 2 Cl 8 ] have been measured at 5 K. Principal band maxima are observed at 14 180 ( z ), 30870 ( xy ), and 39 215 ( z ) cm −1 . The calculation, observed polarizations, and a comparison of band positions in Re 2 Cl 8 2− and Re 2 Br 8 2− suggest the following transition assignments for the former complex: 14 180 cm −1 , b 2g δ → b 1u δ*; 30 870 cm −1 , e g → b 1u δ*; 39 215 cm −1 , e u π → e g π*.