Differences in the Existence States of Hydrogen in UO2 and PuO2 from DFT + U Calculations

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• 作者：Bingyun Ao ; Ruizhi Qiu ; Haiyan Lu ; Piheng Chen
• 刊名：Journal of Physical Chemistry C
• 出版年：2016
• 出版时间：August 25, 2016
• 年：2016
• 卷：120
• 期：33
• 页码：18445-18451
• 全文大小：393K
• 年卷期：0
• ISSN：1932-7455

文摘

First-principles DFT + U methods are performed to calculate the formation energy and to determine the relative stability of hydrogen at the different sites of UO₂ and PuO₂. Twenty-one incorporation sites for hydrogen, i.e., along the pathway from its first nearest-neighboring oxygen to the octahedral interstitial site, are considered. The results indicate that hydrogen in UO₂ energetically prefers to exist as a hydride ion ([(UO₂)_n]⁺H^–) rather than forming a hydroxyl group ([U_nO_2n–1]⁺[OH]⁻). The negative formation energy of hydrogen at the octahedral interstitial site of UO₂ shows that hydrogen is soluble and can oxidize uranium ion to the higher valence states. However, hydrogen in PuO₂ is relatively stable in the form of [Pu_nO_2n–1]⁺[OH]⁻ with comparison to [(PuO₂)_n]⁺H^–. The slightly positive formation energy of hydrogen in the form of the hydroxyl group in PuO₂ reveals that hydrogen is either insoluble or just lies on the edge of solubility. The differences in the existence states of atomic hydrogen in the two dioxides are proposed to be dependent on the nature of 5f electrons of uranium and plutonium; that is, uranium 5f electrons are more delocalized and more favorable to participate in chemical bonding than plutonium 5f electrons.