Chemical reactions in liquids: Molecular dynamics simulation for sulfur
Chemical reactions in liquids: Molecular dynamics simulation for sulfur
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液体中的化学反应：硫的分子动力学模拟
DOI：
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发表时间：
1986
期刊：
影响因子：
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通讯作者：
R. LaViolette
中科院分区：
文献类型：
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作者：
F. Stillinger;T. Weber;R. LaViolette
选择了两原子和三原子相互作用的组合来表示硫的结构化学。该模型可能表现出二价性（键饱和），并导致已知的锡分子形成皱环结构的偏好。利用这种相互作用的表示，在实验液体密度下对1000个硫原子进行了分子动力学计算。对由S8环分子组成的低温液体进行了短时序的计算，并与现有的（不精确的）测量结果在质量上一致。在升高的温度下，模拟中的环状S8分子开始破裂，随后的化学反应主要产生线性聚合物。在聚合过程中发现了一个亚稳反应中间体，一个由双自由基链弱连接在S8环上的“蝌蚪”。
A combination of two‐atom and three‐atom interactions has been selected to represent the structural chemistry of sulfur. This model potential exhibits divalency (bond saturation) and leads to the known preference for Sn molecules to form puckered ring structures. Using this representation of the interactions, molecular dynamics calculations have been performed for 1000 sulfur atoms at the experimental liquid density. Short‐range order has been calculated for the low‐temperature liquid consisting of S8 cyclic molecules, and agrees qualitatively with the (imprecise) available measurements. At elevated temperatures the cyclic S8 molecules in the simulation begin to break open, and their subsequent chemical reactions yield primarily linear polymeric species. A metastable reaction intermediate in the polymerization process has been identified, a ‘‘tadpole’’ consisting of a diradical chain attached weakly to an S8 ring.