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Nonlinear response in oligomers across chain lengths

Caroline Raepsaet1,*, Christiane Alba-Simionesco2, Cécile Wiertel-Gasquet1, and François Ladieu1

  • *Contact author: caroline.raepsaet@cea.fr
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Phys. Rev. Research 7, 043244 – Published 2 December, 2025

DOI: https://doi.org/10.1103/35b2-ysz4

Abstract

We present third-order and first-order dielectric measurements on a series of N-propylene glycol (N-PG) oligomers, focusing on the role of molecular length N in the glass transition. To avoid polymeric effects, we restricted the study to short chains (N=1–20). Linear dielectric susceptibility Δχ1 scales as 1N, suggesting that only the terminal hydroxyl (–OH) groups contribute significantly to the dipolar response, while the flexible backbone units remain largely inactive. Third-order susceptibilities χ3(3) exhibit a growing hump upon cooling for all N-PG, consistent with the Bouchaud-Biroli prediction. This allows us to extract the relative evolution of the number of dynamically correlated molecules Ncorr, which is as expected increasing upon cooling. But surprisingly, this evolution is identical across all oligomers, regardless of chain length, even though the size of the largest molecules likely exceeds that of the dynamic heterogeneities. This robustness of the relative evolution of Ncorr(τα) allows to deduce that it is insensitive to the backbone linking the monomers, the fragility, the OH-bond density, or the strength of the dipole-dipole interactions among oligomers, standard criteria to describe the phenomenon. These findings challenge kinetically constrained models, which fail to account for the observed behavior, while supporting the predictions of the random first-order transition theory.

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Phys. Rev. Research 7, 043244– Published 2 December, 2025
  • Received 11 July 2025
  • Accepted 4 November 2025
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