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Many-body signatures of dimensional reduction in quasi-one-dimensional ZrS3

Marco Campetella* and Letizia Chiodo

  • *Contact author: m.campetella@unicampus.it
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Phys. Rev. B 114, 225125 – Published 14 October, 2026

DOI: https://doi.org/10.1103/vfpp-dm6l

Abstract

The electronic and optical properties of quasi-one-dimensional transition-metal trichalcogenides remain largely unexplored beyond the mean-field approximation, and it is not clear how they evolve as the crystal is thinned. By performing first-principles many-body perturbation theory calculations, we determine the quasiparticle band structures and the polarization-resolved optical response of ZrS3 in the bulk, bilayer, and monolayer limits, using a hierarchy of methods (hybrid DFT, GW, and the Bethe-Salpeter equation). We find that all three systems are indirect-gap semiconductors with a quasidirect character, the direct-indirect splitting being δ≈0.10–0.13eV and nearly independent of both the level of theory and the dimensionality. The mean-field gaps are almost insensitive to thickness, whereas the quasiparticle corrections increase the gap by ≈0.9eV from bulk to monolayer. The effective exact-exchange fraction reproducing the GW gap scales as α∼ɛ∞−1, increasing from ≈0.19 to ≈0.33, so that no single hybrid functional describes the full dimensional series. The optical onset blueshifts monotonically (≈2.4→2.8→3.0eV) and the near-edge absorption is strongly dichroic. A change in light polarization does not simply shift the excitonic resonance (≈0.09eV); it also reorganizes the underlying excitonic wave function, selecting distinct band channels and k-space regions. A real-space, participation-ratio analysis resolves moderately delocalized, Wannier-Mott-like excitons templated along the covalent chains. They are predominantly sulfur-derived (75%–88% of the density on sulfur for the chain-polarized bulk states), which identifies them as (S2)2− disulfide excitations rather than S→Zr charge-transfer states, while in the bilayer the electron delocalizes across both layers, the real-space imprint of interlayer screening. These results provide a consistent reference for the quasiparticle and excitonic energy scales of ZrS3 from the bulk to the few-layer limit.

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Phys. Rev. B 114, 225125– Published 14 October, 2026
  • Received 31 July 2026
  • Revised 25 September 2026
  • Accepted 1 October 2026
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Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.

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