Forty four stationary points have been located on the lowest singlet and triplet potential energy surfaces Of S2N2. Ten minima and ten saddle points on the lowest singlet surface and eleven minima and thirteen saddle points on the lowest triplet surface were found. All saddle points were connected to minima or lower-order saddle points by following the intrinsic reaction coordinate. Renner-Teller effects in the linear isomers were studied by examining their bending curves. The S2N2 polymerization mechanism was investigated by first locating the transition state corresponding to ring opening and then considering all species connected to it that are close in energy. The commonly accepted mechanism is problematic due to the number of species that would lead to dissociation to SN + SN. Other possible isomers that are consistent with the experimental evidence but do not connect to SN radicals in the dissociation limit were examined. A mechanism of polymerization to (SN), is proposed that involves excitation of the square planar singlet molecule to the triplet surface. The triplet species then undergoes a puckering, and polymerization occurs in a direction approximately perpendicular to the S2N2 plane. Consideration of the predicted vibrational frequencies suggests the structure of the second isomer of S2N2. This isomer has a trans-NSSN structure with a long SS bond. The energetics of trans-NSSN are consistent with the observed temperature effects in the dimerization of SN. Analysis of the bending curves of linear NSSN and NSNS indicates that trans-NSSN is the only isomer which has a small yet significant barrier to that dimerization.