Fernández Rodríguez, BertaRodríguez Riego, RafaelRizzo, AntonioQuiñoá Cabana, EmilioRiguera Vega, RicardoFreire Iribarne, Félix Manuel2019-06-172019-06-172018B. Fernández, R. Rodríguez, A. Rizzo, E. Quiñoá, R. Riguera, F. Freire, Angew. Chem. Int. Ed. 2018, 57, 36661433-7851http://hdl.handle.net/10347/18878This is the peer reviewed version of the following article: B. Fernández, R. Rodríguez, A. Rizzo, E. Quiñoá, R. Riguera, F. Freire, Angew. Chem. Int. Ed. 2018, 57, 3666, which has been published in final form at https://doi.org/10.1002/anie.201713164. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.The calculated ECD spectrum (time‐dependent density functional theory TD‐DFT) for small oligomers of polyphenylacetylenes (PPAs) show a very good match with the experimental spectra of the PPA polymers, particularly with the first Cotton band associated to the helical sense of the internal polyenic backbone. This has been proven with a series of PPAs representative of cis‐cisoidal, cis‐transoidal, compressed and stretched polyene backbones, with identical or opposite internal/external rotational senses and allows the prediction of the helical sense of the internal helix of a PPA directly from its CD spectraeng© 2018 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived VersionsHelical SenseElectron Circular DichroismPoly(phenylacetylene)sComputational StudyTD-DFTjournal article10.1002/anie.2017131641521-3773open access