在11组复合体和纳米集群中的金属-联体键
Maryam Sabooni Asre Hazer1, Sami Malola2, Hannu Häkkinen1,2,3
1Department of Chemistry, Nanoscience Center, University of Jyväskylä, FI-40014 Jyväskylä, Finland. hannu.j.hakkinen@jyu.fi.
Physical chemistry chemical physics : PCCP
|July 16, 2024
概括
密度函数理论显示,黄金 (Au) 在金属连接体系统中表现出最高的结合能. 连接物选择对11组金属复合物和集群的稳定性产生重大影响,素和NHC保护的铜 (Cu) 集群显示出高稳定性.
科学领域:
- 计算化学是一种计算化学.
- 材料科学是一种材料科学.
- 无机化学 无机化学 无机化学
背景情况:
- 了解金属 - 连接体相互作用对于设计稳定的金属复合体和集群至关重要.
- 十一组金属 (Cu,Ag,Au) 和各种配体 (硫酸盐,,N-异环碳酸盐,) 是催化和材料科学的关键组成部分.
- 预测这些系统的稳定性和特性需要准确的理论方法.
研究的目的:
- 研究11组金属复合体和集群中的金属联体键的几何,能量和电子特性.
- 阐明不同连接体对这些系统的稳定性和结合特性的影响.
- 为了确定稳定的金属集群形成的最佳连接物组合.
主要方法:
- 密度函数理论 (DFT) 的计算.
- 标准通用梯度近似 (GGA) 理论水平与PBE函数.
- 包含使用BEEF-vdW函数的范德瓦尔斯 (vdW) 校正.
- 对预测状态密度 (PDOS) 和分子轨道 (MO) 的分析.
主要成果:
- 黄金 (Au) 显示了最高的结合能,其次是铜 (Cu) 和银 (Ag).
- 在整个复合体和集群中,债券长度遵循了Ag-L > Au-L > Cu-L的顺序.
- 子侧组在集群中影响了结合能 (最小的NHC侧组产生了最高的能量),但在复合体中没有显著的影响.
- M-酸盐键表现出 σ 和 π 特性,而素和碳素则形成 σ 键;基尼尔配体表现出多种结合 (CCMe 的 σ 和 π,CCPH 的 σ 键).
- 两个不同的配体的复合体中的协同效应增强了结合强度.
结论:
- 连接物选择对11组金属复合体和集群的稳定性产生了关键影响.
- 由 (PPh3) 和N-异环碳 (NHC) 保护的铜 (Cu) 集群非常稳定,仅次于黄金 (Au) 集群.
- 这些发现为设计具有量身定制属性的新金属连接体系统提供了洞察力.
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