Dissociative electron attachment in the (CH3)3SiNSNSi(CH3)3 thiazyl chain

Measurements of the total and of the mass selected anion currents arising from electron attachment in gas-phase (CH3)3SiNSNSi(CH3)3, precursor of the (SN)x polymer, are reported as a function of the impinging electron energy in the 0–6 eV energy range. Abundant production of long-lived molecular anions and of negative fragments at zero energy is associated with the formation of a (vibrationally excited) stable π∗ anion state. In agreement, B3LYP/6-311G∗ calculations predict a positive (0.49 eV) vertical electron affinity. Electron attachment into the π∗ LUMO at zero energy and into the lowest empty σ∗ orbitals around 3.1 eV decays along dissociative channels which involve cleavage of the SN bond, indicating that the small thiazyl chain is prone to dissociation upon electron addition.