过渡金属团簇成键特征的理论研究

过渡金属原子拥有活性的、五重简并的 d 轨道，在它们形成团簇的时候呈现 了相对主族元素更加丰富的结构与反应性质。这使得其团簇在生命过程里（如在 辅酶中）起到至关重要的作用，尤其表现在对惰性小分子（如氮气，甲烷）的温和 条件转化中。 由于 d 轨道的能量、占据数和轨道半径的区别，不同过渡金属的成键特性迥 异，形成团簇的倾向与稳定性也有很大不同。本论文首先分析不同过渡金属原子 的 d 轨道特征和简单的成键情况。接下来选取了不同组分、结构的过渡金属团簇 进行密度泛函理论（Density Functional Theory, DFT）计算研究，包括实验上已经 成功合成分离的：由三个稀土金属（Ln3）形成的离子卡宾化合物（IonicCarbenes） 和由含钨，硫配体稳定的Fe13团簇。通过对DFT计算得到的平均场的基态波函数 和能量进行成键分析，导出具有化学意义的图像，并阐明金属团簇内禀的稳定化 效应和配体对过渡金属团簇支持和稳定作用。进一步地，研究团簇的成键特征与 组分金属的 d 轨道性质的关联性，总结构效关系。 基于过渡金属 d 轨道特征的认识与理解，团簇形成规律的理解，我们预测了 呈正二十面构型的 PtHf12的存在并给出了支持其稳定存在的理论依据，对设计合 成具有新型结构与性质的过渡团簇可以起到一定理论指导作用

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