Decomposition of ferrocene on Pt(111) and its effect on molecular electronic junctions

Reimers, Jeffrey R., Wang, Yin, and Kosov, Daniel S. (2019) Decomposition of ferrocene on Pt(111) and its effect on molecular electronic junctions. Journal of Physical Chemistry Part C, 123. pp. 15569-15574.

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Abstract

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.

Item ID: 59050
Item Type: Article (Research - C1)
ISSN: 1932-7455
Funders: National Natural Science Foundation of China (NNSFC), National Computational Infrastructure, Shanghai High-End Foreign Talents Programme
Projects and Grants: NNSFC grant no. 11674212
Date Deposited: 21 Aug 2019 02:24
FoR Codes: 02 PHYSICAL SCIENCES > 0204 Condensed Matter Physics > 020406 Surfaces and Structural Properties of Condensed Matter @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970102 Expanding Knowledge in the Physical Sciences @ 100%
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