钚表面钝化层抗氢蚀机理的微观动力学模拟

doi:10.3866/PKU.WHXB2014Ac16

摘要/Abstract

摘要：

采用基于范德华密度泛函的vdW-DF(+U)方法, 通过系统的第一性原理电子结构计算和分子动力学模拟, 研究了两种钚钝化层(PuO₂和PuN)的表面电子结构性质, 以及表面与H₂分子相互作用的微观动力学行为.结果显示: (1) H₂很难靠近PuO₂表面, 与表面发生"碰撞-解离"的几率很小, 自钝化层PuO₂具有抗氢蚀作用; 但是, 一方面H₂解离后H原子在PuO₂表面的吸附放热稳定, 另一方面在缺氧条件下PuO₂薄层会转化成α-Pu₂O₃,而H₂能穿过α-Pu₂O₃到达钚层, 所以PuO₂的抗氢蚀性能并不可靠. (2) H₂在PuN表面的微观动力学行为与在PuO₂表面类似, H₂极难解离且H原子的吸附热力学上不稳定; 相对于PuO₂, PuN的成分单一、稳定而且结构致密, PuN具有比PuO₂更好的抗氢蚀性能. 我们希望本工作能为钚表面钝化防护技术的发展提供理论基础和依据.

关键词: 表面钝化, 钚氧化物, 钚氮化物, 表面氢蚀, 第一性原理分子动力学

Abstract:

Based on the non-local van der Waals density functional (vdW-DF)+U scheme, we have performed a first-principles molecular dynamics (FPMD) study of the interaction dynamics for H₂ impingement against the Pu oxide (PuO₂) and Pu nitride (PuN) passivation layers on Pu metal surface. Results show that, except for weak physisorption, both the PuO₂ and PuN surfaces are so difficult to access that almost all of the H₂ molecules will bounce back to the vacuum when their initial kinetic energies are not sufficient. Although dissociative adsorption of H₂ on PuO₂ surfaces is found to be very exothermic, the collision-induced dissociation barriers of H₂ are calculated to be very high. Unfortunately, PuO₂ can be reduced to α-Pu₂O₃ under oxygen-lean conditions. Molecular H₂ can easily penetrate and diffuse in α-Pu₂O₃, and, as a result, α-Pu₂O₃ can promote the hydrogenation of Pu metal. Unlike PuO₂, PuN is found to be a stable and uniform passivation layer against hydrogen-corrosion of Pu, and the interacting system of PuN and H is shown to be thermodynamically unstable. Overall, the current study reveals the different hydrogen-corrosion resistances of PuO₂ and PuN passivation layers, which have implications for the interpretation of experimental observations and will be helpful to understand the surface corrosion and passivation of Pu metal.

Key words: Surface passivation, Plutonium oxide, Plutonium nitride, Surface hydrogen-corrosion, First-principles molecular dynamics

MSC2000:

O647

孙博, 刘海风, 宋海峰, 郑晖. 钚表面钝化层抗氢蚀机理的微观动力学模拟[J]. 物理化学学报, 2015, 31(Suppl): 81-89.

SUN Bo, LIU Hai-Feng, SONG Hai-Feng, ZHENG Hui. Microdynamics Simulations of the Hydrogen-Corrosion Resistance of Passivation Layers on Pu Surface[J]. Acta Phys. -Chim. Sin., 2015, 31(Suppl): 81-89.

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