Figure shows that the Mulliken charge on the sulfur atom tends towards -1 e for r > r min , confirming the S-C β bond fission process to be heterolytic and that the negative charge is localized on the sulfur atom as r increases, as expected. Energetic maxima in the PES scans were reopti- mized to a first-order saddle point to obtain transition states and reaction barriers. We were unable to acquire correct transition states for the Θ min ≈ 310 • rotamers; given that ∆G min for this rotamer is quite close to zero, it is possible that the reaction pathway is smoother without an energetic barrier to overcome, and there might not exist a distinct, well-defined transition state for this rotamer.