García Arcos, CarlosToledano Sanz, ÓscarSanz Monasterio, MikelGálvez González, Óscar2025-10-012025-10-012025-10-27Carlos G. Arcos, Oscar Toledano, Mikel Sanz, Oscar Gálvez, Energetics and structural characterization of Poly(trifluoroethylene) from first principles calculations, Polymer, Volume 337, 2025, 128934, ISSN 0032-3861, https://doi.org/10.1016/j.polymer.2025.1289340032-3861https://doi.org/10.1016/j.polymer.2025.128934https://hdl.handle.net/20.500.14468/30295The registered version of this article, first published in “Polymer, Volume 337, 2025, is available online at the publisher's website: Elsevier, https://doi.org/10.1016/j.polymer.2025.128934 La versión registrada de este artículo, publicado por primera vez en “Polymer, Volume 337, 2025", está disponible en línea en el sitio web del editor: Elsevier, https://doi.org/10.1016/j.polymer.2025.128934Proyecto de investigación: TED2021131914B-I00 Research Project, funded by MCIN/AEI/10.13039/ 501100011033 and by ‘‘ERDF A way of making Europe’In this paper a comprehensive first-principles investigation of the structural and energetic stability of poly(trifluoroethylene) (PTrFE) is reported. Using density functional theory (DFT), we systematically analyze the conformational energetics of PTrFE across three structural levels: isolated molecules, infinite polymer strands, and crystalline solids. Various tacticities—atactic, isotactic, and syndiotactic—are explored for each of the known PVDF phases (𝛼, 𝛽, 𝛾) and the 31 helical structure. Our results reveal that while the isotactic 31 helix is the most stable conformation, planar 𝛽 and 𝛾 phases become energetically favorable in atactic or syndiotactic crystalline environments, where intermolecular interactions and steric minimization dominate. In addition, simulated X-ray diffraction (XRD) patterns are compared with those found in the literature, revealing characteristic features to distinguish different phases and chain arrangements.eninfo:eu-repo/semantics/openAccess33 Ciencias TecnológicasartículoPoly(trifluoroethylene)PTrFEDFTAb initioX-ray diffractionTacticityCrystalline structure