Spontaneous Breaking and Remaking of the RS-Au-SR Staple in Self-assembled Ethylthiolate/Au(111) Interface
Spontaneous Breaking and Remaking of the RS-Au-SR Staple in Self-assembled Ethylthiolate/Au(111) Interface
复制标题
自组装硫醇乙酯/Au(111)界面中RS-Au-SR钉的自发断裂和重建
DOI：
10.1021/acs.jpcc.8b04157
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发表时间：
2018-08-30
影响因子：
3.7
通讯作者：
Guo, Quanmin
中科院分区：
文献类型：
--
作者：
Gao, Jianzhi;Li, Fangsen;Guo, Quanmin
用扫描隧道显微镜(STM)结合密度泛函理论(DFT)和MD计算研究了室温下RS-Au-SR(R=CH2CH3)/Au(111)自组装界面的稳定性。RS-Au-SR订书钉，也称为Au-Au-二硫酸盐，沿着[11(2)Over bar]方向组装成订书针排。STM成像显示，虽然订书针行能够保持静态的全局结构，但行内的单个订书针受到Au-SR键的不断断裂和重建。C2S-Au-SC2/Au(111)界面处于动态平衡状态，远不是刚性的。DFT/MD计算表明，当在RS-Au-SR基团中加入一个自由Au原子时，可以形成一个瞬时的RS-Au-Au-SR络合物。RS-Au-SR基团在室温下具有较高的反应性，可以解释硫代保护的Au纳米团簇的反应性，如参与配体交换和簇间反应的能力。
The stability of the self-assembled RS-Au-SR (R = CH2CH3)/Au(111) interface at room temperature has been investigated using scanning tunneling microscopy (STM) in conjunction with density functional theory (DFT) and MD calculations. The RS-Au-SR staple, also known as Au-adatom-dithiolate, assembles into staple rows along the [11 (2) over bar] direction. STM imaging reveals that while the staple rows are able to maintain a static global structure, individual staples within the row are subjected to constant breaking and remaking of the Au-SR bond. The C2S-Au-SC2/Au(111) interface is under a dynamic equilibrium and it is far from rigid. DFT/MD calculations show that a transient RS-Au-Au-SR complex can be formed when a free Au atom is added to the RS-Au-SR staple. The relatively high reactivity of the RS-Au-SR staple at room temperature could explain the reactivity of thiolate-protected Au nanoclusters, such as their ability to participate in ligand exchange and intercluster reactions.