Dynamics of Charged Species in Ionic-Neutral Block Copolymer and Surfactant Complexes

JM Borreguero and PA Pincus and BG Sumpter and M Goswami, JOURNAL OF PHYSICAL CHEMISTRY B, 121, 6958-6968 (2017).

DOI: 10.1021/acsjpcb.7b05047

Structure property relationships of ionic block copolymer (BCP) surfactant complexes are critical toward the progress of favorable engineering design of efficient charge-transport materials. In this article, molecular dynamics simulations are used to understand the dynamics of charged-neutral BCP and surfactant complexes. The dynamics are examined for two different systems: charged -neutral double- hydrophilic and hydrophobic hydrophilic block copolymers with oppositely charged surfactant moieties. The dynamics of the surfactant head, tails, and charges are studied for five different BCP volume fractions. We observe that the dynamics of the different species solely depend on the balance between electrostatic and entropic interactions between the charged species and the neutral monomers. The favorable hydrophobic hydrophobic interactions and the unfavorable hydrophobic hydrophilic interactions determine the mobilities of the monomers. The dynamical properties of the charge species influence complex formation. Structural relaxations exhibit length-scale dependent behavior, with slower relaxation at the radius of gyration length-scale and faster relaxation at the segmental length-scale, consistent with previous results. The dynamical analysis correlates ion-exchange kinetics to the self-assembly behavior of the complexes.

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