| 吴博,黄静梦,谭桂珍,郝志峰,胡光辉,罗继业,崔成强.化学通报,2021,84(6):610-619. |
| 基于密度泛函理论研究碱性水溶液中乙内酰脲及其衍生物的结构及性质 |
| DFT Study on the Structure and Properties of Hydantoin and Its Derivatives in the Alkaline Aqueous Solution |
| 投稿时间：2020-10-13 修订日期：2020-12-26 |
| DOI： |
| 中文关键词: 乙内酰脲 密度泛函理论 络合剂 分子表面分析 |
| 英文关键词:Hydantoin Density functional theory Complexing agent Molecular surface analysis |
| 基金项目:国家自然科学基金项目（61874155）资助 |
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| 中文摘要: |
| 乙内酰脲及其衍生物对多种金属离子具有良好的络合效果，是一种有望取代氰化物的绿色电镀络合剂。本文以密度泛函理论（DFT）方法对乙内酰脲及其衍生物的反应活性进行了研究。通过分子极性指数和极性表面积所占总面积百分比研究多种乙内酰脲衍生物在水中的溶解性，理论计算结果与文献报道的实验结果基本一致。通过原子电荷、表面静电势、原子对最高占据分子轨道的贡献、平均局部离子化能和简缩局部软度考察去质子化后的各原子的配位能力，其中含S原子的2-硫代乙内酰脲（TH）比其他衍生物具有更强的配位能力，其可能是有研究前景的无氰络合剂。通过解离常数预测各衍生物达到去质子化状态的难易程度。AIM拓扑分析表明所研究的分子结构稳定性较好，而在373K下的分子动力学模拟表明，1，3-二羟甲基-5，5-二甲基乙内酰脲（DMDMH）热稳定性较差，其他分子热稳定性较好。 |
| 英文摘要: |
| Hydantoin and its derivatives, which have strong complexing effects with various metal ions, are expected to replace cyanide as green electroplating complexing agents. Density functional theory (DFT) was used to study the reactivity of hydantoin and its derivatives. The solubility of these derivatives in water was studied by using the molecular polarity index and the percentage of polar surface area in the total area. The results of theoretical calculation were basically consistent with the experimental results reported previously and indicated that the studied molecules have good solubility in water and have significance for further study. Atomic charge, molecular electrostatic potential, composition of the main atoms for HOMO, average local ionization energy and condensed local softness were used to investigate the coordination ability of the atoms of the deprotonated molecules comprehensively. The results revealed that S atom in 2-thiohydantoin (TH) had the most negative atomic charge, showing strong electrostatic interactions with metal ions. In addition, the degree of difficulty for each derivative to reach the deprotonation state was predicted by dissociation constant. The topological analysis based on AIM showed that the molecular structure was stable, while the molecular dynamics simulation at 373K showed that the thermodynamic stability of 1,3-dihydroxy methyl-5,5-dimethyl hydantoin(DMDMH) was poor and other molecules' were good. |
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