聚硫化染色体物种在索达利特群矿物中的相互转换:关于S6分解的DFT研究
Maria Fedyaeva1,2, Sergey Lepeshkin1,2,3, Nikita V Chukanov4
1Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, Kosygina, 19, Moscow, 119991, Russia.
循环硫-6 (S6) 分子的衰变,对于矿色彩至关重要,是由电子捕获启动的. 密度函数模拟揭示了关键的衰变路径和能量障碍,解释了观察到的矿物质颜色变化.
科学领域:
- 矿物学和材料科学 矿物学和材料科学
- 计算化学的计算化学
- 固态化学 固态化学
背景情况:
- 聚硫化物种是众所周知的色彩决定因素,可见于石组矿物质中,如海,拉苏里特和斯卢迪安卡特.
- 这些聚硫化物的热转化会引起颜色变化,但基本机制仍然不太清楚.
- 循环硫-6 (S6) 分子是这些转换相关的一个突出例子.
研究的目的:
- 使用计算模拟,阐明循环S6分子的衰变机制.
- 为了确定S6的初级衰变路径和最终反应产物.
- 了解电子捕获在促进S6分解中的作用及其对矿物质颜色的影响.
主要方法:
- 密度功能理论 (DFT) 模拟被用来探索S6分子的衰变路径.
- 计算的重点是确定最可能的反应产物,例如S3⋅-+S3⋅-和S2⋅-+S4⋅-基离子对.
- 确定了不同反应步骤的能量障碍,包括电子捕获.
主要成果:
- 对S6最有利的衰变途径涉及一个电子的初始捕获,大大降低了环开放所需的能量.
- 由此产生的链基离子的分解具有约0.4 eV的限制能量屏障.
- 发现Sn⋅- (n=2-6) 基离子在相同的硫链长度下比其他电荷状态更稳定.
结论:
- 电子捕获是一个关键的初始步骤,促进中性聚硫化物分子的衰变,包括S6.
- 计算的能量障碍和反应产物与实验观察索达利特组矿物质的热转换相一致.
- 这项研究提供了对多硫化物转化如何影响索达矿物质颜色的机制理解.
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