Kinetic control of molecular assembly on surfaces
Kinetic control of molecular assembly on surfaces
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DOI：
10.1038/s42004-018-0069-0
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发表时间：
2018-10
影响因子：
5.9
通讯作者：
Chiara Paris;A. Floris;S. Aeschlimann;J. Neff;F. Kling;A. Kühnle;L. Kantorovich
中科院分区：
文献类型：
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作者：
Chiara Paris;A. Floris;S. Aeschlimann;J. Neff;F. Kling;A. Kühnle;L. Kantorovich
通常认为沉积在表面上的分子具有最稳定的结构。在这里，我们表明，通过考虑一个模型系统的二羟基苯甲酸分子的方解石（10.4）表面上，亚稳态的分子结构也可以通过选择一个合适的初始状态的分子定义所观察到的转换路径，而且，我们证明，后者是完全由动力学控制，而不是热力学。我们认为，分子沉积的二聚体，经历了一系列的结构转变，从集群有序条纹，然后密集的网络，最后到无序的结构。结合高分辨率的动态原子力显微镜实验和密度泛函理论计算，我们提供了一个全面的分析，驱动这一序列的过渡的基本原则。我们的研究可能会开辟新的途径，动力学控制的基础上，作为一个有前途的战略，实现定制的分子结构的表面。
It is usually assumed that molecules deposited on surfaces assume the most thermodynamically stable structure. Here we show, by considering a model system of dihydroxybenzoic acid molecules on the (10.4) surface of calcite, that metastable molecular architectures may also be accessed by choosing a suitable initial state of the molecules which defines the observed transformation path. Moreover, we demonstrate that the latter is entirely controlled by kinetics rather than thermodynamics. We argue that molecules are deposited as dimers that undergo, upon increase of temperature, a series of structural transitions from clusters to ordered striped and then dense networks, and finally to a disordered structure. Combining high-resolution dynamic atomic force microscopy experiments and density-functional theory calculations, we provide a comprehensive analysis of the fundamental principles driving this sequence of transitions. Our study may open new avenues based on kinetic control as a promising strategy for achieving tailored molecular architectures on surfaces.