As it has been shown earlier, DIB molecules are preferably connected via short sulfur chains (n ≃ 4). Here, we consider DIB-S 4 -DIB and DIB-S 8 -DIB as target molecules in vacuum representing local structures of poly(sulfur-n-1,3-diisopropenylbenzene) containing short and long S chains, respectively. The connection of the sulfur chains and the DIB molecules are assumed to be via a quaternary carbon. For the sake of comparison, we also consider gas-phase S 4 and S 8 chains with terminal sulfur atoms saturated with hydrogens.