• ISSN 2097-1893
    • CN 10-1855/P

    氦在地幔斯石英中迁移的第一性原理研究

    First-Principles Study of Helium Migration in Stishovite in the Earth's Mantle

    • 摘要: 本研究利用密度泛函理论(DFT)和Climbing Image Nudged Elastic Band(CI-NEB)过渡态计算方法,探究了地球地幔条件下氦(He)在无水与含水斯石英中的扩散机制. 在无水斯石英中,He的扩散受限于结构开放的001通道,其他方向的扩散活化能显著高于该方向,印证了He在无水斯石英中仅沿001通道迁移的特征. 然而,由于含水斯石英中存在“一维超离子通道”,在该通道内,He扩散活化能不足无水斯石英的一半(<50%),这显著提升了He的迁移速率. 在压力效应方面,尽管压力升高会同步增加两类斯石英的扩散能垒,但含水斯石英表现出更弱的压力敏感性,即压力增加50 GPa时,其He扩散速率的下降程度远低于无水斯石英. 另外,温度依赖性滞留分析表明,无水斯石英的He滞留温度响应滞后于含水斯石英,这类似于石英相对于柯石英的规律:在相同He滞留水平下,石英比柯石英能承受更高的温度. 这些发现揭示了晶体结构特征(无水斯石英的001方向通道与含水斯石英的超离子通道)对稀有气体迁移动力学的决定性作用. 通过量化压力-温度-颗粒尺寸对He扩散的调控,本研究推进了地下稀有气体循环及地球深部脱气过程的机理模型.

       

      Abstract: The migration mechanisms of helium in anhydrous and hydrous stishovite under Earth's mantle conditions is studied using density functional theory (DFT) and climbing image nudged elastic band (CI-NEB) transition state calculations. In anhydrous stishovite, He diffusion is constrained to the structurally unobstructed 001 channels, with diffusion activation energies along other directions significantly higher than 001, confirming that He migrates almost exclusively through these anisotropic pathways. Hydrous stishovite, however, hosts "one-dimensional superionic conduits", where the activation energy for He diffusion is less than 50% of that in anhydrous stishovite, leading to markedly enhanced He diffusion rate. Pressure exerts a similar effect on both stishovite types—increasing pressure elevates diffusion energy barriers and reduces He diffusion rates. However, hydrous stishovite exhibits weaker pressure sensitivity: a 50 GPa pressure increase causes a far smaller reduction in He diffusion rates compared to anhydrous stishovite. Temperature-dependent retention analysis further reveals that anhydrous stishovite exhibits delayed thermal responsiveness relative to hydrous stishovite, mirroring the trend observed between quartz and coesite—under equivalent He retention levels, quartz sustains higher temperatures than coesite. These findings underscore the decisive role of crystal structural features, specifically, the 001 channels in anhydrous stishovite and superionic conduits in hydrous stishovite are governing noble gas migration dynamics. By quantifying the modulation of He diffusion by pressure, temperature, and grain size, this work advances mechanistic models for subsurface noble gas cycling and deep Earth degassing processes.

       

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