Temperature-Dependent Conformation Behavior of Isolated Poly(3-hexylthiopene) Chains

Abstract

We use atomistic as well as coarse-grained molecular dynamics simulations to study the conformation of a single poly(3-hexylthiopene) chain as a function of temperature. We find that mainly bundle and toroid structures appear with bundles becoming more abundant for decreasing temperatures. We compare an atomistic and a Martini-based coarse-grained model which we find in very good agreement. We further illustrate how the temperature dependence of P3HT can be connected to that of simple Lennard–Jones model polymers in a vacuum. Upon adding solvent (THF) we observe the occurrence of a prominent swelling of the molecular size at a temperature of about 220 K. This swelling is in close agreement with the interpretation of recent spectroscopic experiments (Panzer et al. J Phys Chem Lett 8, 114 (2017)) which allows us to explain the experimental observations by an increased frequency of bundle structures.