The Disappearing Quartz-Coesite Path: the Phase Transition Mechanism of Silicon Dioxide from Machine Learning Simulations
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摘要: 基于高维神经网络势能模型与随机表面行走算法，系统研究了二氧化硅在高压条件下的结构相变机理。首先，构建了覆盖石英、柯石英、斯石英及非晶态的全局势能面，绘制出热力学相图。进一步分析发现，对于石英到斯石英的相变路径，高压下能垒显著降低，表现出较强的动力学可行性；而柯石英至斯石英的相变路径则为单步机制，能垒随压力升高略有上升。在非晶化相变方面，通过采样与识别低对称性结构群，明确了低对称性结构群在石英高压非晶化中的关键作用，揭示了“短程有序—中程无序—拓扑有序”结构作为非晶态的关键特征。值得注意的是，研究过程中未发现有效的石英-柯石英相变路径，进一步研究表明，非晶路径在动力学上的优势“截断”了石英向柯石英的直接演化路径，揭示了石英-柯石英路径缺失的本质原因。该工作系统探究了高压下二氧化硅的晶态与非晶态相变机理，为复杂氧化物的高压模拟研究提供了理论依据和方法范式。Abstract: This study systematically investigates the structural phase transition mechanisms of silicon dioxide under high pressure by using the high-dimensional neural network potential model combined with the stochastic surface walking algorithm. First, a global potential energy surface of quartz, coesite, stishovite, and amorphous states was constructed, and the thermodynamic phase diagram reveals the thermodynamic stability advantage of stishovite in high-pressure regions. Further analysis demonstrated that the energy barrier for the quartz-to-stishovite transition path shows a significant decrease under high pressure, which exhibits strong kinetic feasibility; while for the coesite-to-stishovite pathway, it follows a single transition state mechanism and the energy barrier displays a slightly increase under high pressure. Regarding the amorphization transition, the low symmetry structure group plays a key role in the high-pressure amorphization of quartz based on sampling and identification, and the “short-range order−middle range-disorder−topological order” structure was unveiled as a defining characteristic of the amorphous state. Notably, we did not observe effective quartz-coesite transition path during the study and further confirmed that the advantage of kinetic dynamics in the amorphization transition inhibits this transformation pathway, revealing the origin of the absence of the quartz-coesite transition. This work systematically explores the mechanisms of crystalline and amorphous phase transitions in silicon dioxide under high pressure and provides theoretical foundations and methodological paradigms for high-pressure simulation studies of complex oxides.
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图 3 石英至斯石英相变路径与能垒分析
Figure 3. Phase transition pathway and energy barrier analysis from quartz to stishovite
图 5 柯石英至斯石英的相变路径与能垒分析
Figure 5. Phase transition pathway and energy barrier analysis from coesite to stishovite
图 8 石英至非晶相S1的相变路径、能垒及配位数分析
Figure 8. Phase transition pathway, energy barriers and coordination numbers from quartz to S1
图 10 柯石英和斯石英相对于石英的相对能量随压力的变化关系
Figure 10. Relative energies of coesite and stishovite as a function of pressure (relative to quartz)
图 11 柯石英与SLS在势能面上的位置关系
Figure 11. Locations of coesite and SLS on the potential energy surface
表 1 石英至斯石英的相变在不同压力下的能量分析
Table 1. Energy of the quartz-to-stishovite phase transition under different pressures
Pressure/GPa Energy barrier/[eV/(f. u.)] Final state energy/[eV/(f. u.)] 5 0.793 0.118 10 0.581 −0.225 15 0.402 −0.510 20 0.261 −0.752 
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表 2 柯石英至斯石英的相变在不同压力下的能量分析
Table 2. Energy of the coesite-to-stishovite phase transition under different pressures
Pressure/GPa Energy barrier/[eV/(f. u.)] Final state energy/[eV/(f. u.)] 10 0.107 −0.160 15 0.118 −0.165 20 0.127 −0.169
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表 3 石英至S1的相变在不同压力下的能量分析
Table 3. Energy of the quartz-to-S1 phase transition under different pressures
Pressure/GPa Energy barrier/[eV/(f. u.)] Final state energy/[eV/(f. u.)] 5 0.597 0.452 10 0.462 0.341 15 0.296 0.240 20 0.119 0.111
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