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

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 cy...

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Autores principales:	Fabian Pieck, Ralf Tonner-Zech
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	density functional theory pEDA organic functionalization silicon surface nudged elastic band ab initio molecular dynamics Organic chemistry QD241-441
Acceso en línea:	https://doaj.org/article/9f99e2fe447e4358a580c3d5d52717ad
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spelling	oai:doaj.org-article:9f99e2fe447e4358a580c3d5d52717ad2021-11-11T18:37:14ZAlkyne-Functionalized Cyclooctyne on Si(001): Reactivity Studies and Surface Bonding from an Energy Decomposition Analysis Perspective10.3390/molecules262166531420-3049https://doaj.org/article/9f99e2fe447e4358a580c3d5d52717ad2021-11-01T00:00:00Zhttps://www.mdpi.com/1420-3049/26/21/6653https://doaj.org/toc/1420-3049The 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.Fabian PieckRalf Tonner-ZechMDPI AGarticledensity functional theorypEDAorganic functionalizationsilicon surfacenudged elastic bandab initio molecular dynamicsOrganic chemistryQD241-441ENMolecules, Vol 26, Iss 6653, p 6653 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	density functional theory pEDA organic functionalization silicon surface nudged elastic band ab initio molecular dynamics Organic chemistry QD241-441
spellingShingle	density functional theory pEDA organic functionalization silicon surface nudged elastic band ab initio molecular dynamics Organic chemistry QD241-441 Fabian Pieck Ralf Tonner-Zech Alkyne-Functionalized Cyclooctyne on Si(001): Reactivity Studies and Surface Bonding from an Energy Decomposition Analysis Perspective
description	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.
format	article
author	Fabian Pieck Ralf Tonner-Zech
author_facet	Fabian Pieck Ralf Tonner-Zech
author_sort	Fabian Pieck
title	Alkyne-Functionalized Cyclooctyne on Si(001): Reactivity Studies and Surface Bonding from an Energy Decomposition Analysis Perspective
title_short	Alkyne-Functionalized Cyclooctyne on Si(001): Reactivity Studies and Surface Bonding from an Energy Decomposition Analysis Perspective
title_full	Alkyne-Functionalized Cyclooctyne on Si(001): Reactivity Studies and Surface Bonding from an Energy Decomposition Analysis Perspective
title_fullStr	Alkyne-Functionalized Cyclooctyne on Si(001): Reactivity Studies and Surface Bonding from an Energy Decomposition Analysis Perspective
title_full_unstemmed	Alkyne-Functionalized Cyclooctyne on Si(001): Reactivity Studies and Surface Bonding from an Energy Decomposition Analysis Perspective
title_sort	alkyne-functionalized cyclooctyne on si(001): reactivity studies and surface bonding from an energy decomposition analysis perspective
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/9f99e2fe447e4358a580c3d5d52717ad
work_keys_str_mv	AT fabianpieck alkynefunctionalizedcyclooctyneonsi001reactivitystudiesandsurfacebondingfromanenergydecompositionanalysisperspective AT ralftonnerzech alkynefunctionalizedcyclooctyneonsi001reactivitystudiesandsurfacebondingfromanenergydecompositionanalysisperspective
_version_	1718431777809235968

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

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