Formation of radical cations of para-substituted polystyrenes in dichloroethane by electron beam pulse irradiation

• Electron pulse radiolysis experiments and quantum chemical calculations clarified the dynamics of polystyrene derivative radical cations in 1,2-dichloroethane. • The radical cation of poly(4-methoxystyrene) has a characteristic lifetime ( t ₁/₂ = 680 μs), which is three orders of magnitude longer than that of polystyrene at 298 K. • The impact of substituent size on the multimer radical cations in the PS derivatives is shown.