Band Structure Modulation of ZrO2 Nanoparticles for Control of CO Adsorption Properties: A Combined Density Functional Theory - Density Functional Tight Binding Study
Abstract
We present a combined density functional theory (DFT) and density functional tight binding (DFTB) study of zirconia (ZrO2) nanoparticles of experimentally relevant sizes of several nanometers and their interactions with the CO molecule. A hybrid DFTB - Force Field (DFTB-FF) framework is developed, whereby band structure calculations rely on an existing Slater-Koster framework, while the accuracy of structural optimization and adsorption properties is controlled by the introduction of classical long-range interatomic potentials into DFTB instead of the traditional repulsive potentials. Additionally, coordination-dependent Zr-C potentials are introduced to account for the distinct local chemical environments of bulk-like facet sites and under-coordinated tip and edge sites, thereby improving the description of CO adsorption. This hybrid DFTB-FF approach substantially improves the robustness of geometry optimization and provides a practical strategy for extending the applicability of DFTB to complex oxide nanostructures. The calculations reveal that termination stoichiometry can be used to engineer intrinsic, p-type, or n-type electronic structures and thereby tune the adsorption activity of zirconia nanoparticles. While stoichiometric nanoparticles do not activate the C-O bond, low-coordinated sites in Zr-rich (n-type) nanoparticles exhibit chemisorption accompanied by charge donation into a CO antibonding LUMO-derived orbital, resulting in C-O bond activation. These results demonstrate that stoichiometry-controlled electronic structure and under-coordinated surface sites introduced by nanostructuring play a key role in governing the adsorption strength and reactivity of zirconia nanoparticles.
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BibTeX
@misc{chen2026band,
title = {{Band Structure Modulation of ZrO2 Nanoparticles for Control of CO Adsorption Properties: A Combined Density Functional Theory - Density Functional Tight Binding Study}},
author = {Kexin Chen and William Dawson and Aulia Sukma Hutama and Takahito Nakajima and Keisuke Kameda and Manabu Ihara and Sergei Manzhos},
howpublished = {arXiv},
year = {2026},
month = sep,
doi = {10.48550/arxiv.2609.08329},
eprint = {2609.08329},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2609.08329},
note = {CC BY-NC-ND 4.0},
}
RIS
TY - UNPB
TI - Band Structure Modulation of ZrO2 Nanoparticles for Control of CO Adsorption Properties: A Combined Density Functional Theory - Density Functional Tight Binding Study
AU - Kexin Chen
AU - William Dawson
AU - Aulia Sukma Hutama
AU - Takahito Nakajima
AU - Keisuke Kameda
AU - Manabu Ihara
AU - Sergei Manzhos
PY - 2026
DA - 2026/09/08
PB - arXiv
DO - 10.48550/arxiv.2609.08329
UR - https://arxiv.org/abs/2609.08329
AB - We present a combined density functional theory (DFT) and density functional tight binding (DFTB) study of zirconia (ZrO2) nanoparticles of experimentally relevant sizes of several nanometers and their interactions with the CO molecule. A hybrid DFTB - Force Field (DFTB-FF) framework is developed, whereby band structure calculations rely on an existing Slater-Koster framework, while the accuracy of structural optimization and adsorption properties is controlled by the introduction of classical long-range interatomic potentials into DFTB instead of the traditional repulsive potentials. Additionally, coordination-dependent Zr-C potentials are introduced to account for the distinct local chemical environments of bulk-like facet sites and under-coordinated tip and edge sites, thereby improving the description of CO adsorption. This hybrid DFTB-FF approach substantially improves the robustness of geometry optimization and provides a practical strategy for extending the applicability of DFTB to complex oxide nanostructures. The calculations reveal that termination stoichiometry can be used to engineer intrinsic, p-type, or n-type electronic structures and thereby tune the adsorption activity of zirconia nanoparticles. While stoichiometric nanoparticles do not activate the C-O bond, low-coordinated sites in Zr-rich (n-type) nanoparticles exhibit chemisorption accompanied by charge donation into a CO antibonding LUMO-derived orbital, resulting in C-O bond activation. These results demonstrate that stoichiometry-controlled electronic structure and under-coordinated surface sites introduced by nanostructuring play a key role in governing the adsorption strength and reactivity of zirconia nanoparticles.
ER -