Vibrational Fingerprints of Strained Polymers: A Spectroscopic Pathway to Mechanical State Prediction

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Main Authors: Konrad, Julian, Mittelhaus, Janina, Wilkins, David M., Fiedler, Bodo, Meißner, Robert
Format: Preprint
Published: 2025
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author Konrad, Julian
Mittelhaus, Janina
Wilkins, David M.
Fiedler, Bodo
Meißner, Robert
author_facet Konrad, Julian
Mittelhaus, Janina
Wilkins, David M.
Fiedler, Bodo
Meißner, Robert
contents The vibrational response of polymer networks under load provides a sensitive probe of molecular deformation and a route to non-destructive diagnostics. Here we show that machine-learned force fields reproduce these spectroscopic fingerprints with quantum-level fidelity in realistic epoxy thermosets. Using MACE-OFF23 molecular dynamics, we capture the experimentally observed redshifts of para-phenylene stretching modes under tensile load, in contrast to the harmonic OPLS-AA model. These shifts correlate with molecular elongation and alignment, consistent with Badger's rule, directly linking vibrational features to local stress. To capture IR intensities, we trained a symmetry-adapted dipole moment model on representative epoxy fragments, enabling validation of strain responses. Together, these approaches provide chemically accurate and computationally accessible predictions of strain-dependent vibrational spectra. Our results establish vibrational fingerprints as predictive markers of mechanical state in polymer networks, pointing to new strategies for stress mapping and structural-health diagnostics in advanced materials.
format Preprint
id arxiv_https___arxiv_org_abs_2509_16266
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Vibrational Fingerprints of Strained Polymers: A Spectroscopic Pathway to Mechanical State Prediction
Konrad, Julian
Mittelhaus, Janina
Wilkins, David M.
Fiedler, Bodo
Meißner, Robert
Chemical Physics
Materials Science
Machine Learning
The vibrational response of polymer networks under load provides a sensitive probe of molecular deformation and a route to non-destructive diagnostics. Here we show that machine-learned force fields reproduce these spectroscopic fingerprints with quantum-level fidelity in realistic epoxy thermosets. Using MACE-OFF23 molecular dynamics, we capture the experimentally observed redshifts of para-phenylene stretching modes under tensile load, in contrast to the harmonic OPLS-AA model. These shifts correlate with molecular elongation and alignment, consistent with Badger's rule, directly linking vibrational features to local stress. To capture IR intensities, we trained a symmetry-adapted dipole moment model on representative epoxy fragments, enabling validation of strain responses. Together, these approaches provide chemically accurate and computationally accessible predictions of strain-dependent vibrational spectra. Our results establish vibrational fingerprints as predictive markers of mechanical state in polymer networks, pointing to new strategies for stress mapping and structural-health diagnostics in advanced materials.
title Vibrational Fingerprints of Strained Polymers: A Spectroscopic Pathway to Mechanical State Prediction
topic Chemical Physics
Materials Science
Machine Learning
url https://arxiv.org/abs/2509.16266