Detaching thiolates from copper and gold clusters

Which bonds to break?

Martin Konôpka, Roger Rousseau, Ivan Štich, Dominik Marx

Research output: Contribution to journalArticle

81 Citations (Scopus)

Abstract

The interaction of alkanethiolates with small coinage metal clusters of copper and gold was studied based on density functional theory with a focus on the metal-thiolate junction. Calculation of fragmentation energies indicate that for Cun-thiolate (n = 1,3,5,7, and 9) there is a progressive lowering in energy for the fragmentation of the S-C bond in the thiolate from a value of 2.9 eV for n = 1 to 1.4 eV for n = 9. The detailed electronic origins of this specific weakening are attributed to a polarization of electron density in the S-C bond as induced by bonding with the Cun cluster. For the gold analogues, this effect is not observed and fragmentation at the S-C bond experiences only a slight 10% destabilization as n increases from 3 to 9. The relativistic origin of this difference between Cu and Au is discussed, and an analysis of bonding considerations is presented.

Original languageEnglish
Pages (from-to)12103-12111
Number of pages9
JournalJournal of the American Chemical Society
Volume126
Issue number38
DOIs
Publication statusPublished - Sep 29 2004

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Gold
Copper
Coinage
Metals
Density functional theory
Carrier concentration
Electrons
Polarization

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Detaching thiolates from copper and gold clusters : Which bonds to break? / Konôpka, Martin; Rousseau, Roger; Štich, Ivan; Marx, Dominik.

In: Journal of the American Chemical Society, Vol. 126, No. 38, 29.09.2004, p. 12103-12111.

Research output: Contribution to journalArticle

Konôpka, Martin ; Rousseau, Roger ; Štich, Ivan ; Marx, Dominik. / Detaching thiolates from copper and gold clusters : Which bonds to break?. In: Journal of the American Chemical Society. 2004 ; Vol. 126, No. 38. pp. 12103-12111.
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