The formation of [C(SH)(3)](+) (a) by hydride abstraction from HC(SH)(3) and its oxidation to the radical dication [C(SH)(3)](.,2+) (b) were studied to examine the potential of stabilizing carbenium ions via trithio substitution. Potential energy surfaces (PES) were explored at the HF/6-31G* level and energies were refined at the (P)MP4-(full,sdtq)/6-31G* level without and with annihilation of spin contaminations. The unpaired pi-electron in the radical lies well below the Fermi level and spin polarization and dynamic electron correlation become important. Open Y-conjugated structures 1 (C-3h or C-s) and their rotamers 2 (C-s) are favored. Four cyclic, S-S connected, distonic, chiral stereoisomers 3b are local minima for the radical dication. The C-S rotational barriers to isomerization via 4 and automerization via 5 (two isomeric TSs) and the high energies of C-3v models 6 indicate stronger S-C pi-interactions in the cations 1 and 2 than in the dications. C-3h-1b undergoes a Jahn-Teller distortion to C-5-1b’ but pseudorotation is facile.