STRUCTURE OF OXIDIZED DISULFIDE BONDS AS CALCULATED BY THE CNDO/2 METHOD

Abstract

ONDO/2 calculations indicate that disulfide cation radicals, e.g. HSSH⁺ and CH₃SSCH₃ ⁺, have a trans-planar structure in contrast to the twisted structure of the parent molecule. The main reason for this difference is the removal of an electron from the sulfur lone-pair orbitals. The bond energy in the disulfide cation radical is much lower than in the parent molecule, which makes the reaction CH₃SSCH₃ ⁺ → CH₃S→ + CH₃S⁺ allowed, as observed previously in radiolysis of CH₃SSCH₃ single crystals.