Helically Enhanced Chiroptical Response and Symmetry Breaking in Conjugated Polymers

Chiral $\pi$-conjugated polymers are an attractive material platform for spin polarized carrier-transport and spectroscopy, but fundamental considerations for how torsional disorder influences the response properties of the material have not been considered. Here we combine atomistic electronic structure modeling with with experimental spectroscopic measurements to examine symmetry breaking in the prototypical $\pi$-conjugated polymer polyacetylene, (CH)$_x$. Chiral (CH)$_x$ oligomers are generated in distinct conformations which differ in their out-of-plane tonsorial ordering. We find that a \textit{helical }conformation introduces orders of magnitude enhanced chiroptical activity due to a solenoid effect. This effect is visualized by the Transition Chiral Tensor analysis which shows signatures of domain ordering which eliminates destructive interference between electric and magnetic contributions. These findings highlight the capability to develop a hierarchical interpretation relating local, fragment symmetry breaking to global, nonlocal interactions governing chiroptical response in emerging chiral materials.