Theoretical investigation of thermodynamic stability and mobility of the oxygen vacancy in ThO2–UO2 solid solutions

Literature Information

Publication Date 2014-10-16
DOI 10.1039/C4CP03660C
Impact Factor 3.676
Authors

B. Liu, D. S. Aidhy


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Abstract

The thermodynamic stability and the migration energy barriers of oxygen vacancies in ThO2–UO2 solid solutions are investigated by density functional theory calculations. In pure ThO2, the formation energy of the oxygen vacancy is 7.58 eV and 1.46 eV under O rich and O poor conditions, respectively, while its migration energy barrier is 1.97 eV. The addition of UO2 into ThO2 significantly decreases the energetics of formation and migration of the oxygen vacancy. Among the range of UO2–ThO2 solid solutions studied in this work, UO2 exhibits the lowest formation energy (5.99 eV and −0.13 eV under O rich and O poor conditions, respectively) and Th0.25U0.75O2 exhibits the lowest migration energy barrier (∼1 eV). Furthermore, by considering chemical potential, the phase diagram of the oxygen vacancy as a function of both temperature and oxygen partial pressure is shown, which could help to gain experimental control over oxygen vacancy concentration.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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