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Effect of quantum anharmonic ionic fluctuations on the bond length alternation and giant piezoelectricity of conjugated polymers

Stefano Paolo Villani1,*, Lorenzo Monacelli1, Paolo Barone2, and Francesco Mauri1

  • 1Dipartimento di Fisica, Università di Roma La Sapienza, Piazzale Aldo Moro 5, 00185 Roma, Italy
  • 2CNR-SPIN Institute for Superconducting and other Innovative Materials and Devices, Area della Ricerca di Tor Vergata, Via del Fosso del Cavaliere 100, I-00133 Rome, Italy

  • *Contact author: stefano.villani@uniroma1.it
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Phys. Rev. B 114, 074101 – Published 3 August, 2026

DOI: https://doi.org/10.1103/nw5j-flyl

Abstract

Functionalized conjugated polymers are promising materials for electromechanical applications due to predicted giant piezoelectricity arising from anomalously large dynamical effective charges combined with an enhanced response near a dimerization phase transition. In this work, we further establish their potential by assessing the robustness of the piezoelectric response of a prototypical polymer against potentially detrimental quantum ionic fluctuations. We use the stochastic self-consistent harmonic approximation with a Rice-Mele diatomic chain model, parametrized to reproduce hybrid-functional first-principles calculations. Despite quantum fluctuations in the bond length reaching magnitudes comparable to the average value, the strong piezoelectric response persists. The topological enhancement of the effective charges remains robust and is even enhanced by about 20% thanks to a quantum-induced shrinking of the electronic gap. The piezoelectric coefficient remains dominated by the internal relaxation and retains a morphotropic-like character, reaching maximum values near the phase boundary renormalized by quantum fluctuations. Our results contribute to pushing forward functionalized conjugated polymers as a promising platform for high-performance organic piezoelectrics.

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Phys. Rev. B 114, 074101– Published 3 August, 2026
  • Received 31 March 2026
  • Revised 5 July 2026
  • Accepted 14 July 2026
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