Decomposition of Ferrocene on Pt(111) and Its Effect on Molecular Electronic Junctions

Reimers, JR; Wang, Y; Kosov, DS

Decomposition of Ferrocene on Pt(111) and Its Effect on Molecular Electronic Junctions

Reimers, JR

Wang, Y Kosov, DS

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Publication Type:: Journal Article
Citation:: Journal of Physical Chemistry C, 2019
Issue Date:: 2019-01-01

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Field	Value	Language
dc.contributor.author	Reimers, JR https://orcid.org/0000-0001-5157-7422	en_US
dc.contributor.author	Wang, Y	en_US
dc.contributor.author	Kosov, DS	en_US
dc.date.available	2020-05-25T19:05:06Z
dc.date.issued	2019-01-01	en_US
dc.identifier.citation	Journal of Physical Chemistry C, 2019	en_US
dc.identifier.issn	1932-7447	en_US
dc.identifier.uri	http://hdl.handle.net/10453/135056
dc.description.abstract	© 2019 American Chemical Society. From dilute vapor, ferrocene encountering Pt(111) decomposes, producing bound cyclopentadienyl rings, in contrast to its legendary stability in solution electrochemistry. We propose that decomposition occurs through initial chemisorption, making a Pt-C bond to a ferrocenium hydride, followed by step-edge catalyzed decomposition leading to migration of the Fe atom inside the Pt bulk. These conclusions are based on results from density functional theory (DFT) calculations. When Pt(111) approaches ferrocene tethered to a self-assembled monolayer, only the first, spontaneous but mechanically reversible chemisorption is predicted. Nonequilibrium Green's function calculations utilizing DFT predict that chemisorption increases molecular junction conductivities by a factor of 2-5. This could contribute to the extremely high conductivities observed in junctions supporting rectification up to unprecedented high-frequency cutoffs of ∼520 GHz, though squashed junctions at half monolayer coverage are predicted to conduct 104 times better.	en_US
dc.relation.ispartof	Journal of Physical Chemistry C	en_US
dc.relation.isbasedon	10.1021/acs.jpcc.9b02628	en_US
dc.subject.classification	Physical Chemistry	en_US
dc.title	Decomposition of Ferrocene on Pt(111) and Its Effect on Molecular Electronic Junctions	en_US
dc.type	Journal Article
utslib.for	0306 Physical Chemistry (incl. Structural)	en_US
utslib.for	03 Chemical Sciences	en_US
utslib.for	09 Engineering	en_US
utslib.for	10 Technology	en_US
pubs.embargo.period	Not known	en_US
pubs.organisational-group	/University of Technology Sydney
pubs.organisational-group	/University of Technology Sydney/Faculty of Science
pubs.organisational-group	/University of Technology Sydney/Faculty of Science/School of Mathematical and Physical Sciences
utslib.copyright.status	open_access
pubs.publication-status	Published	en_US

Abstract:

© 2019 American Chemical Society. From dilute vapor, ferrocene encountering Pt(111) decomposes, producing bound cyclopentadienyl rings, in contrast to its legendary stability in solution electrochemistry. We propose that decomposition occurs through initial chemisorption, making a Pt-C bond to a ferrocenium hydride, followed by step-edge catalyzed decomposition leading to migration of the Fe atom inside the Pt bulk. These conclusions are based on results from density functional theory (DFT) calculations. When Pt(111) approaches ferrocene tethered to a self-assembled monolayer, only the first, spontaneous but mechanically reversible chemisorption is predicted. Nonequilibrium Green's function calculations utilizing DFT predict that chemisorption increases molecular junction conductivities by a factor of 2-5. This could contribute to the extremely high conductivities observed in junctions supporting rectification up to unprecedented high-frequency cutoffs of ∼520 GHz, though squashed junctions at half monolayer coverage are predicted to conduct 104 times better.

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http://hdl.handle.net/10453/135056