Modeling Calcite Crystallization on Self-Assembled Carboxylate-Terminated Alkanethiols

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• 作者：Alexander S. C么t茅 ; Robert Darkins ; Dorothy M. Duffy
• 刊名：Journal of Physical Chemistry C
• 出版年：2014
• 出版时间：August 21, 2014
• 年：2014
• 卷：118
• 期：33
• 页码：19188-19193
• 全文大小：420K
• ISSN：1932-7455

文摘

We systematically investigate the crystallization of calcite on self-assembled monolayers (SAMs) composed of carboxylate-terminated alkanethiols of various lengths using molecular dynamics simulation and employing metadynamics to accelerate the process. The (012) calcite surface is found to nucleate on all SAMs, irrespective of the monolayer length. Our simulations provide insight into the growth and structure of the calcite/SAM interface. In particular, we identify point defects at the interface as playing a crucial role in quenching the net dipole moment and accommodating the poor epitaxial match. Step formation also readily occurs as a means of reducing the calcite-monolayer lattice mismatch. The (012)/SAM interface was shown to have a higher energy than the (001)/SAM interface, which had an excellent epitaxial match; therefore, (012) nucleation is assumed to be a kinetic effect.