Hydrogen Bonding in Parascorodite and Relative Stability of Fe(AsO4)⋅2H2O Polymorphs

IF 0.8 4区地球科学 Q3 GEOLOGY Geology of Ore Deposits Pub Date : 2024-02-07 DOI:10.1134/s1075701523070061

S. V. Krivovichev

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Abstract

Density functional theory (DFT) has been used with CRYSTAL14 program to optimize hydrogen atom positions in the crystal structure of parascorodite Fe(AsO₄)⋅2H₂O. It has been shown that taking into account hydrogen bonding, the structure forms six-membered asymmetrical cycles –Fe1–O1–H1^…O3–As–O2– and eight-membered cycles –Fe1–O1–H2^…O2–Fe1–O2^…H2–O1– with lateral topological symmetry. Calculation of the structural complexity parameters for scorodite and parascorodite and their comparison with thermodynamic characteristics shows that the Fe(AsO₄)⋅2H₂O polymorph modifications correspond well to Goldsmith’s rule that states that metastable transitional polymorphs are structurally simpler than thermodynamically stable phases. Scorodite is a stable phase, whereas parascorodite is metastable, which agrees well with the conclusions made in the previous works. Crystallization of parascorodite under natural conditions of oxidation zones of ore-mineral deposits may occur due to the high speed of its nucleation as a metastable phase, i.e., due to the kinetic stabilization of its structure.

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副沸石中的氢键和 Fe(AsO4)⋅2H2O 多晶体的相对稳定性

摘要利用密度泛函理论（DFT）和 CRYSTAL14 程序优化了副菱镁矿 Fe(AsO4)⋅2H2O 晶体结构中的氢原子位置。结果表明，考虑到氢键，该结构形成了具有横向拓扑对称性的六元不对称循环-Fe1-O1-H1...O3-As-O2-和八元循环-Fe1-O1-H2...O2-Fe1-O2...H2-O1-。通过计算蝎尾石和副蝎尾石的结构复杂性参数并将其与热力学特征进行比较，可以发现Fe(AsO4)⋅2H2O的多晶体修饰非常符合戈德史密斯法则，即蜕变过渡多晶体的结构比热力学稳定相简单。烁石是稳定相，而副烁石是可迁移相，这与前人的研究结论十分吻合。在矿石矿床氧化区的自然条件下，副闪长岩的结晶可能是由于其作为可转移相的成核速度快，即由于其结构的动力学稳定性。

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来源期刊

Geology of Ore Deposits 地学-地质学

CiteScore

1.10

自引率

14.30%

发文量

审稿时长

6-12 weeks

期刊介绍： Geology of Ore Deposits is a periodical covering the topic of metallic and nonmetallic mineral deposits, their formation conditions, and spatial and temporal distribution. The journal publishes original scientific articles and reviews on a wide range of problems in theoretical and applied geology. The journal focuses on the following problems: deep geological structure and geodynamic environment of ore formation; distribution pattern of metallogenic zones and mineral deposits; geology and formation environment of large and unique metallic and nonmetallic deposits; mineralogy of metallic and nonmetallic deposits; physicochemical and isotopic characteristics and geochemical environment of ore deposition; evolution of ore-forming systems; radiogeology and radioecology, economic problems in exploring, developing, and mining of ore commodities.