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Van der Waals molecular interactions in the organic functionalization of graphane, silicane, and germanane with alkene and alkyne molecules: a DFT-D2 study

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Abstract

Density functional theory with the addition of a semi-empirical dispersion potential was applied to the conventional Kohn–Sham energy to study the adsorption of alkene and alkyne molecules on hydrogen-terminated two-dimensional group IV systems (graphane, silicane, and germanane) by means of a radical-initiated reaction. In particular, we investigated the interactions of acetylene, ethylene, and styrene with those surfaces. Although we had studied these systems previously, we included van der Waals interactions in all of the cases examined in the present work. These forces, which are noncovalent interactions, can heavily influence different processes in molecular chemistry, such as the adsorption of organic molecules on semiconductor surfaces. This unified approach allowed us to perform a comparative study of the relative reactivities of the various organic molecule/surface systems. The results showed that the degree of covalency of the surface, the lattice size, and the partial charge distribution (caused by differences in electronegativity) are all key elements that determine the reactivity between the molecules and the surfaces tested in this work. The covalent nature of graphane gives rise to energetically favorable intermediate states, while the opposite polarities of the charge distributions of silicane and germanane with the organic molecules favor subsequent steps of the radical-initiated reaction. Finally, the lattice size is a factor that has important consequences due to steric effects present in the systems and the possibility of chain reaction continuation. The results obtained in this work show that careful selection of the substrate is very important. Calculated energy barriers, heats of adsorption, and optimized atomic structures show that the silicane system offers the best reactivity in organic functionalization.

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Acknowledgments

We are grateful for financial support from Conacyt Project 164485 and DGAPA project IN100516. Calculations were performed in the DGCTIC-UNAM supercomputing center (project SC16-1-IG-31).

All of the authors contributed to the writing of the manuscript. All of the authors also gave their approval to the final version of the manuscript

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Authors and Affiliations

  1. Centro de Investigación Científica y de Educación Superior de Ensenada 3918, Código Postal 22860, Ensenada, Baja California, Mexico

    Pamela Rubio-Pereda

  2. Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, Apartado Postal 14, Código Postal 22800, Ensenada, Baja California, Mexico

    Noboru Takeuchi

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  1. Pamela Rubio-Pereda
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  2. Noboru Takeuchi
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Correspondence to Pamela Rubio-Pereda.

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Rubio-Pereda, P., Takeuchi, N. Van der Waals molecular interactions in the organic functionalization of graphane, silicane, and germanane with alkene and alkyne molecules: a DFT-D2 study. J Mol Model 22, 175 (2016). https://doi.org/10.1007/s00894-016-3048-3

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