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Article

Alkyne-Functionalized Cyclooctyne on Si(001): Reactivity Studies and Surface Bonding from an Energy Decomposition Analysis Perspective

Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, 04103 Leipzig, Germany
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Academic Editors: Carlo Gatti, Maxim L. Kuznetsov, David L. Cooper and Miroslav Kohout
Molecules 2021, 26(21), 6653; https://doi.org/10.3390/molecules26216653
Received: 30 September 2021 / Revised: 26 October 2021 / Accepted: 27 October 2021 / Published: 2 November 2021
The reactivity and bonding of an ethinyl-functionalized cyclooctyne on Si(001) is studied by means of density functional theory. This system is promising for the organic functionalization of semiconductors. Singly bonded adsorption structures are obtained by [2 + 2] cycloaddition reactions of the cyclooctyne or ethinyl group with the Si(001) surface. A thermodynamic preference for adsorption with the cyclooctyne group in the on-top position is found and traced back to minimal structural deformation of the adsorbate and surface with the help of energy decomposition analysis for extended systems (pEDA). Starting from singly bonded structures, a plethora of reaction paths describing conformer changes and consecutive reactions with the surface are discussed. Strongly exothermic and exergonic reactions to doubly bonded structures are presented, while small reaction barriers highlight the high reactivity of the studied organic molecule on the Si(001) surface. Dynamic aspects of the competitive bonding of the functional groups are addressed by ab initio molecular dynamics calculations. Several trajectories for the doubly bonded structures are obtained in agreement with calculations using the nudged elastic band approach. However, our findings disagree with the experimental observations of selective adsorption by the cyclooctyne moiety, which is critically discussed. View Full-Text
Keywords: density functional theory; pEDA; organic functionalization; silicon surface; nudged elastic band; ab initio molecular dynamics; chemical bonding density functional theory; pEDA; organic functionalization; silicon surface; nudged elastic band; ab initio molecular dynamics; chemical bonding
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MDPI and ACS Style

Pieck, F.; Tonner-Zech, R. Alkyne-Functionalized Cyclooctyne on Si(001): Reactivity Studies and Surface Bonding from an Energy Decomposition Analysis Perspective. Molecules 2021, 26, 6653. https://doi.org/10.3390/molecules26216653

AMA Style

Pieck F, Tonner-Zech R. Alkyne-Functionalized Cyclooctyne on Si(001): Reactivity Studies and Surface Bonding from an Energy Decomposition Analysis Perspective. Molecules. 2021; 26(21):6653. https://doi.org/10.3390/molecules26216653

Chicago/Turabian Style

Pieck, Fabian, and Ralf Tonner-Zech. 2021. "Alkyne-Functionalized Cyclooctyne on Si(001): Reactivity Studies and Surface Bonding from an Energy Decomposition Analysis Perspective" Molecules 26, no. 21: 6653. https://doi.org/10.3390/molecules26216653

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