The role of isomerization in the kinetics of self-assembly: p-terphenyl-m-dicarbonitrile on the Ag(111) surface.
The role of isomerization in the kinetics of self-assembly: p-terphenyl-m-dicarbonitrile on the Ag(111) surface.
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DOI：
10.1039/c5cp00220f
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发表时间：
2015-04
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通讯作者：
David Abbasi-Pérez;J. Recio;L. Kantorovich
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文献类型：
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作者：
David Abbasi-Pérez;J. Recio;L. Kantorovich
使用包括从头算密度泛函理论计算、微移弹性带方法和动力学蒙特卡罗 (KMC) 建模在内的理论技术工具包，我们详细研究了对三联苯间二甲腈 (pTmDC) 分子如何扩散和异构化以在 Ag(111) 表面上自组装。我们证明分子通过旋转机制在表面“行走”，一次移动其两条“腿”。然后，我们确定了一种能够改变分子手性的特殊“底面”异构化机制，并证明它对于理解 Ag(111) 表面上带、连接体、簇和砖墙岛的氢键组装的生长至关重要，正如最近的扫描隧道显微镜实验中所观察到的那样 (ChemPhysChem, 2010, 11, 1446)。所发现的自组装原子机制可能是手性分子在金属表面上其他氢键结构生长的背后。
Using a toolkit of theoretical techniques comprising ab initio density functional theory calculations, the nudged elastic band method and kinetic Monte Carlo (KMC) modeling, we investigate in great detail how para-terphenyl-meta-dicarbonitrile (pTmDC) molecules diffuse and isomerize to self-assemble on the Ag(111) surface. We show that molecules "walk" on the surface via a pivoting mechanism moving each of its two "legs" one at a time. We then identify a peculiar "under-side" isomerization mechanism capable of changing the molecules chirality, and demonstrate that it is fundamental in understanding the growth of hydrogen bonding assembles of ribbons, linkers, clusters and brickwall islands on the Ag(111) surface, as observed in recent scanning tunneling microscopy experiments (ChemPhysChem, 2010, 11, 1446). The discovered underlying atomistic mechanism of self-assembly may be behind the growth of other hydrogen bonding structures of chiral molecules on metal surfaces.