The attempt to prepare hitherto unknown homopolyatomic cations of sulfur by the reaction of elemental sulfur with blue S-8(AsF6)(2) in liquid SO2/SO2CIF, led to red (in transmitted light) crystals identified crystallographically as S-8(AsF6)(2). The X-ray structure of this salt was redetermined with improved resolution and corrected for librational motion: monoclinic, space group P2(1)/c (No. 14), Z = 8, a = 14.986(2) Angstrom, b = 13.396(2) Angstrom, c = 16.351(2) Angstrom, beta = 108.12(1)degrees. The gas phase structures of E-8(2+) and neutral E-8 (E = S, Se) were examined by ab initio methods (B3PW91, MPW1P91) leading to Delta H-f(Theta)[S-8(2+), g] = 2151 kJ/mol and Delta H-t(Theta)[Se-8(2+), g] = 2071 kJ/mol. The observed solid state structures of S-8(2+) and Se-8(2+) with the unusually long transannular bonds of 2.8-2.9 Angstrom were reproduced computationally for the first time, and the E-8(2+) dications were shown to be unstable toward all stoichiometrically possible dissociation products E-n(+) and/or E-4(2+) [n = 2-7, exothermic by 21-207 kJ/mol (E = S), 6-151 kJ/mol (E = Se)]. Lattice potential energies of the hexafluoroarsenate salts of the latter cations were estimated showing that S-8(AsF6)(2) [Se-8(AsF6)(2)] is lattice stabilized in the solid state relative to the corresponding AsF6- salts of the stoichiometrically possible dissociation products by at least 116 [204] kJ/mol. The fluoride ion affinity of AsF5-(g) was calculated to be 430.5 +/- 5.5 kJ/mol [average B3PW91 and MPW1PW91 with the 6-311+G(3df) basis set]. The experimental and calculated FT-Raman spectra of E-8(AsF6)(2) are in good agreement and show the presence of a cross ring vibration with an experimental (calculated, scaled) stretching frequency of 282 (292) cm(-1) for S-8(2+) and 130 (133) cm(-1) for Se-8(2+). An atoms in molecules analysis (AIM) of E-8(2+) (E = S, Se) gave eight bond critical points between ring atoms and a ninth transannular (E3-E7) bond critical point, as well as three ring and one cage critical points. The cage bonding was supported by a natural bond orbital (NBO) analysis which showed, in addition to the Es a-bonded framework, weak n bonding around the ring as well as numerous other weak interactions, the strongest of which is the weak transannular E3-E7 [2.86 Angstrom (S-8(2+)), 2.91 Angstrom (Se-8(2+))] bond. The positive charge is delocalized over all atoms, decreasing the Coulombic repulsion between positively charged atoms relative to that in the less stable Ss-like exo-exo Eg(2+) isomer. The overall geometry was accounted for by the Wade-Mingos rules, further supporting the case for cage bonding. The bonding in Te-8(2+) is similar, but with a stronger transannular E3-E7 (E = Te) bonding. The bonding in E-8(2+) (E = S, Se, Te) can also be understood in terms of a sigma -bonded Eg framework with additional bonding and charge delocalization occurring by a combination of transannular n pi*-n pi* (n = 3, 4, 5), and np(2) --> n sigma* bonding. The classically bonded S-8(2+) (Se-8(2+)) dication containing a short transannular S+-S+ (Se+-Se+) bond of 2.20 (2.57) Angstrom is 29 (6) kJ/mol higher in energy than the observed structure in which the positive charge is delocalized over all eight chalcogen atoms.