Facet- and thickness-dependent band-edge alignment at ZrSe\texorpdfstring{3}{3} surfaces: hybrid-functional calculations with spin-orbit coupling
Abstract
Transition-metal trichalcogenides MX3 are quasi-one-dimensional van der Waals materials whose layers form through lateral chain binding, giving them an interlayer cleavage plane and in-plane electronic anisotropy. Among them, ZrSe3 is stable under ambient conditions and semiconducting. Exfoliated crystals expose four crystallographic planes, and electrocatalytic measurements on an individual crystal assigned the hydrogen evolution activity to the high-energy (210) facet rather than to the basal plane. Those non-basal surfaces remain uncharacterized, since the available calculations treat either the bulk crystal or the free-standing basal monolayer. Here, we compute the surface energies and the equilibrium morphology of these four surfaces with a dispersion-corrected semilocal functional, and their band-edge alignment with the HSE06 hybrid functional including spin-orbit coupling. The surface energies span nearly an order of magnitude, from \SI{0.097}{\joule\per\meter\squared} for (001) to \SI{0.869}{\joule\per\meter\squared} for (010), and the Wulff shape exposes the four observed planes with area fractions of \SI{17.1}{\percent}, \SI{4.4}{\percent}, \SI{71.4}{\percent}, and \SI{7.0}{\percent}. The ionization potential varies by \SI{0.45}{\electronvolt} between facets and the electron affinity by \SI{0.80}{\electronvolt}, the gap of (210) falls from 1.43 to \SI{0.94}{\electronvolt} between 10 and \SI{23}{\angstrom}, and (010) remains metallic. The facets separate according to whether the cut preserves or distorts the Se-Se dimer, and the distorted dimers concentrate the frontier states. Because the same dimer governs the bulk electronic structure of the MX3 family, the criterion transfers to the related trichalcogenides.
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BibTeX
@misc{holanda2026facet,
title = {{Facet- and thickness-dependent band-edge alignment at ZrSe\texorpdfstring$_3$3 surfaces: hybrid-functional calculations with spin-orbit coupling}},
author = {Sandro G Holanda and Bruno Ipaves and Astrid Campos-Mata and Shreyasi Chattopadhyay and Pulickel M Ajayan and Douglas S Galvao and Marcelo L Pereira Junior},
howpublished = {arXiv},
year = {2026},
month = sep,
doi = {10.48550/arxiv.2609.36150},
eprint = {2609.36150},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2609.36150},
note = {CC BY 4.0},
}
RIS
TY - UNPB
TI - Facet- and thickness-dependent band-edge alignment at ZrSe\texorpdfstring{_3}{3} surfaces: hybrid-functional calculations with spin-orbit coupling
AU - Sandro G Holanda
AU - Bruno Ipaves
AU - Astrid Campos-Mata
AU - Shreyasi Chattopadhyay
AU - Pulickel M Ajayan
AU - Douglas S Galvao
AU - Marcelo L Pereira Junior
PY - 2026
DA - 2026/09/28
PB - arXiv
DO - 10.48550/arxiv.2609.36150
UR - https://arxiv.org/abs/2609.36150
AB - Transition-metal trichalcogenides MX_3 are quasi-one-dimensional van der Waals materials whose layers form through lateral chain binding, giving them an interlayer cleavage plane and in-plane electronic anisotropy. Among them, ZrSe_3 is stable under ambient conditions and semiconducting. Exfoliated crystals expose four crystallographic planes, and electrocatalytic measurements on an individual crystal assigned the hydrogen evolution activity to the high-energy (210) facet rather than to the basal plane. Those non-basal surfaces remain uncharacterized, since the available calculations treat either the bulk crystal or the free-standing basal monolayer. Here, we compute the surface energies and the equilibrium morphology of these four surfaces with a dispersion-corrected semilocal functional, and their band-edge alignment with the HSE06 hybrid functional including spin-orbit coupling. The surface energies span nearly an order of magnitude, from \SI{0.097}{\joule\per\meter\squared} for (001) to \SI{0.869}{\joule\per\meter\squared} for (010), and the Wulff shape exposes the four observed planes with area fractions of \SI{17.1}{\percent}, \SI{4.4}{\percent}, \SI{71.4}{\percent}, and \SI{7.0}{\percent}. The ionization potential varies by \SI{0.45}{\electronvolt} between facets and the electron affinity by \SI{0.80}{\electronvolt}, the gap of (210) falls from 1.43 to \SI{0.94}{\electronvolt} between 10 and \SI{23}{\angstrom}, and (010) remains metallic. The facets separate according to whether the cut preserves or distorts the Se-Se dimer, and the distorted dimers concentrate the frontier states. Because the same dimer governs the bulk electronic structure of the MX_3 family, the criterion transfers to the related trichalcogenides.
ER -