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Main Authors: Huang, Yang, Zhang, Le, Ji, Hefei, Zhang, Zhipeng, Zhang, Qili, Sun, Bo, Liu, Haifeng, Song, Haifeng
Format: Preprint
Published: 2025
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Online Access:https://arxiv.org/abs/2502.08078
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author Huang, Yang
Zhang, Le
Ji, Hefei
Zhang, Zhipeng
Zhang, Qili
Sun, Bo
Liu, Haifeng
Song, Haifeng
author_facet Huang, Yang
Zhang, Le
Ji, Hefei
Zhang, Zhipeng
Zhang, Qili
Sun, Bo
Liu, Haifeng
Song, Haifeng
contents Unraveling the adsorption mechanism and thermodynamics of O$_2$ and H$_2$O on uranium dioxide surfaces is critical for the nuclear fuel storage and uranium corrosion. Based on the first-principles DFT+U-D3 calculations, we carefully test the effect of antiferromagnetic order arrangements on the thermodynamic stability of UO$_2$ surfaces and propose the 1k AFM surface computational model. The chemisorption states of O$_2$ and H$_2$O on UO$_2$ (111) surface, suggested by previous experiments, are accurately calculated for the first time. The adsorption properties of O$_2$ and H$_2$O on UO$_2$(111) and (110) surfaces are discussed in detail to reveal the different interaction mechanisms. Combined with ab initio atomistic thermodynamics method, we systematically calculate the chemisorption phase diagram and isotherm of O$_2$ and H$_2$O on UO$_2$ surfaces. Due to the different intermolecular interactions, the monolayer and multilayer adsorption models are identified for O$_2$ and H$_2$O, respectively. This study has comprehensively revealed the different adsorption mechanisms of O$_2$ and H$_2$O on UO$_2$ surfaces, bridging the electronic structure calculations to the interpretation of experimental results and providing a solid foundation for future theoretical studies of uranium corrosion mechanism in humid air.
format Preprint
id arxiv_https___arxiv_org_abs_2502_08078
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle The chemisorption thermodynamics of O$_2$ and H$_2$O on AFM UO$_2$ surfaces unraveled by DFT+U-D3 study
Huang, Yang
Zhang, Le
Ji, Hefei
Zhang, Zhipeng
Zhang, Qili
Sun, Bo
Liu, Haifeng
Song, Haifeng
Materials Science
Computational Physics
Unraveling the adsorption mechanism and thermodynamics of O$_2$ and H$_2$O on uranium dioxide surfaces is critical for the nuclear fuel storage and uranium corrosion. Based on the first-principles DFT+U-D3 calculations, we carefully test the effect of antiferromagnetic order arrangements on the thermodynamic stability of UO$_2$ surfaces and propose the 1k AFM surface computational model. The chemisorption states of O$_2$ and H$_2$O on UO$_2$ (111) surface, suggested by previous experiments, are accurately calculated for the first time. The adsorption properties of O$_2$ and H$_2$O on UO$_2$(111) and (110) surfaces are discussed in detail to reveal the different interaction mechanisms. Combined with ab initio atomistic thermodynamics method, we systematically calculate the chemisorption phase diagram and isotherm of O$_2$ and H$_2$O on UO$_2$ surfaces. Due to the different intermolecular interactions, the monolayer and multilayer adsorption models are identified for O$_2$ and H$_2$O, respectively. This study has comprehensively revealed the different adsorption mechanisms of O$_2$ and H$_2$O on UO$_2$ surfaces, bridging the electronic structure calculations to the interpretation of experimental results and providing a solid foundation for future theoretical studies of uranium corrosion mechanism in humid air.
title The chemisorption thermodynamics of O$_2$ and H$_2$O on AFM UO$_2$ surfaces unraveled by DFT+U-D3 study
topic Materials Science
Computational Physics
url https://arxiv.org/abs/2502.08078