Universal insertion of molecules in ionic compounds under pressure
Universal insertion of molecules in ionic compounds under pressure
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DOI：
10.1093/nsr/nwae016
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发表时间：
2024-01
影响因子：
20.6
通讯作者：
Feng Peng;Yanming Ma;Chris J. Pickard;Hanyu Liu;Maosheng Miao
中科院分区：
文献类型：
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作者：
Feng Peng;Yanming Ma;Chris J. Pickard;Hanyu Liu;Maosheng Miao
摘要利用第一性原理计算和晶体结构搜索方法，我们发现许多共价键分子，如H_2、N_2、CO_2、NH_3、H_2O和CH_4，可以与离子固体原型氯化钠在加压下反应生成稳定的化合物，同时保持其分子结构。这些分子，无论是同核或异核、极性或非极性、小或大，都不会与周围的钠和氯离子表现出强烈的化学相互作用。相反，在所有例子中最稳定的分子，氮，被发现在高压下与−反应时转化为环-N5氯化钠阴离子。这为合成具有高能量密度的绿色能源材料五唑盐提供了一条新的途径。我们的工作展示了一种独特而普遍的共价键分子和固体化合物在压力下的杂交倾向。这种令人惊讶的可混性表明，在大型行星内部的分子层和岩石层之间可能存在混合区域。
ABSTRACT Using first-principles calculations and crystal structure search methods, we found that many covalently bonded molecules such as H2, N2, CO2, NH3, H2O and CH4 may react with NaCl, a prototype ionic solid, and form stable compounds under pressure while retaining their molecular structure. These molecules, despite whether they are homonuclear or heteronuclear, polar or non-polar, small or large, do not show strong chemical interactions with surrounding Na and Cl ions. In contrast, the most stable molecule among all examples, N2, is found to transform into cyclo-N5− anions while reacting with NaCl under high pressures. It provides a new route to synthesize pentazolates, which are promising green energy materials with high energy density. Our work demonstrates a unique and universal hybridization propensity of covalently bonded molecules and solid compounds under pressure. This surprising miscibility suggests possible mixing regions between the molecular and rock layers in the interiors of large planets.