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. 2024 Jul 22;15:6153. doi: 10.1038/s41467-024-50530-7

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© The Author(s) 2024

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

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Fig. 6 — PES schematic showing the processes of vibrational cooling (thermalisation) and polaron pair state formation in thin film of (a) the g0% polymer, which thermalises in 0.6 ps to the minimum of the S₁ state and subsequently forms polaron pairs (labelled PP), thermalising to the minimum of the PP state by 1.25 ps and (b) the g100% polymer, where vibrational coupling facilitates PP formation and the polymer thermalises in 5 ps to the minimum of the PP state. Green arrows indicate measured vibrational cooling times. ΔQ is the offset of the S₀ and S₁ PESs and is larger for the g100% polymer, as shown with the solvatochromic measurements. k_r,0 and k_r,100 are the radiative recombination rates for the g0% and g100% polymers, respectively. The PESs of the g100% polymer are shown to be broader than those of the g0% polymer, which is a result of the higher structural disorder in the polymer^39,70. Source data are provided as a Source Data file.