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We exploited the high temporal and spatial resolution of neutron spin echospectroscopy to investigate the large-scale dynamics of semiflexible conjugatedpolymer chains in solutions. We obtained the first experimental demonstrationof earlier predicted single chain glassy state. We used a generalized approachof the well-established Zimm model of flexible polymers to describe therelaxation mode spectra of locally stiff polythiophene chains. The Zimm modeanalysis confirms the existence of beads with a finite length that correspondsto a reduced number of segmental modes in semiflexible chains. Irrespective ofthe temperature and the molecular weight of the conjugated polymer, we witnessa universal behavior of the local chain stiffness and invariability of thebeads length. Our experimental findings indicate possibly minor role of thechange in {\pi}-electron conjugation length (and therefore conjugated backboneplanar to non-planar conformational transition) in the observed thermochromicbehavior of polythiophene but instead point on the major role of chain dynamicsin this phenomenon.

Impact of Local Stiffness on Entropy Driven Microscopic Dynamics of Polythiophene