Chemisorption and physisorption of alkanethiols on Cu(). A quantum mechanical investigation

Ferral, Anabella; Paredes-Olivera, Patricia A.; Macagno, V. A.; Patrito, E.M.

doi:10.1016/s0039-6028(02)02543-8

Cited by 49 publications

(59 citation statements)

References 77 publications

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“…Therefore, larger metal clusters are required for adsorbates with important charge transfer with the surface. In our previous theoretical work on alkanethiol adsorption on Cu(1 1 1) [31], we showed that for metal clusters of more than 25 atoms, converged binding energies with cluster size are obtained. In the present work, we used a cluster with 25 metal atoms distributed in two layers with 16 and 9 atoms, respectively.…”

Section: Theoretical Methods and Surface Modelingmentioning

confidence: 84%

Reactivity of 1,8-octanedithiol monolayers on Au(111): Experimental and theoretical investigation

Carot

Esplandiu

Cometto

et al. 2005

Journal of Electroanalytical Chemistry

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Section: Theoretical Methods and Surface Modelingmentioning

confidence: 84%

Reactivity of 1,8-octanedithiol monolayers on Au(111): Experimental and theoretical investigation

Carot

Esplandiu

Cometto

et al. 2005

Journal of Electroanalytical Chemistry

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“…The interpretation of STM images of alkanethiols based SAMs is not straightforward [17]. In the case of short chain thiols, like methylthiolate, experiments [18] do not show atomic resolution, while for longer chain thiols it is not clear yet whether a c(4 · 2) or a ð ffiffi ffi 3 p Â ffiffi ffi 3 p ÞR30 superstructure is seen [2].…”

Section: Stm Imagingmentioning

confidence: 99%

Methylthiolate adsorption on Au(111): Energetics, vibrational modes and STM imaging

2006

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“…Theoretical investigation of alkanethiols adsorption indicates that the substrate donates ∼1/2 e-charge to the sulfur atom. 18 With increasing EN of the para substituent (Br, 2.8; Cl, 3; F, 4), more and more charge is pulled to its side. If the substituents in meta/ortho position have a lower EN, then a strong molecular quadrupole moment (QM) results.…”

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confidence: 99%

Effect of Halo Substitution on the Geometry of Arenethiol Films on Cu(111)

et al. 2004

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Thiol films on noble metal surfaces attract considerable interest due to their ability of facile self-assembly from the solution phase. 1 Films of only monomolecular thickness can modify the electronic, physical, and chemical properties of the underlying substrate dramatically. This offers powerful opportunities for fundamental studies of electron transport, 2 single-molecule devices (e.g., tunneling diodes 3 or transistor 4 ), control of surface wettability, 5 etc. The formation of thiol films is driven predominantly by strong substrate-sulfur interactions. At saturation coverage, the result is a layer of molecules that stand close to upright on the surface. For alkanethiols on Au(111), ( 3 x 3)R30°and related superlattices were inferred. [6][7][8] In a solution environment, it is difficult to follow the initial stages of thiol chemisorption because of their high surface mobility prior to formation of a dense film and the presence of the surrounding solution. Vacuum deposition of thiols allows the study of low coverages, and a large variety of different alkanethiols patterns have been reported. [9][10][11][12] To the best knowledge of the authors, low coverages of arenethiols have not been addressed so far, although arenethiols have much larger potential for electronic applications than alkanethiols. This study uses thiophenol (TP) and, and pentafluoro-substituted (5FTP) analogues as model compounds for arenethiol film formation and explores the impact of a slight variation of arenethiol size and substituent electronegativity (EN) on the films' structural properties. We studied a broad range of coverages and found the most dramatic effects at incomplete films, where the molecules aggregate into isolated islands that are separated by empty terraces.We used two home-built STM systems that were operated in UHV (<10 -10 Torr) at cryogenic temperatures (15 or 81 K). Multiple cryopanels enclosed the STMs in order to minimize drift and sample contamination. We used a Cu(111) single crystal as a substrate. Sample preparation involved cycles of sputtering (Ar, 1.5 keV) and annealing (600 K). All arenethiol coverages were prepared by backfilling the chamber to a pressure of ∼10 -9 Torr and (if necessary, multiple cycles of) sample exposure for ∼15 s.We observed spontaneous formation of the superlattices in Figure 1 at 81K, which suggests that they may form transiently during the deposition of larger coverages. Figure 1a,b shows STM images of isolated CTP and TP molecules at 15 K after hydrogen abstraction. The molecules adsorb flat on the surface, and their image has a depression that we associate with the position of the thiol group. Using lateral manipulation 13 and coadsorption of CO for registry, 14 we find that both the S and the halogen atoms occupy Cu(111) hollow sites. The overall shape of FTP, 5FTP, and BTP is similar to Figure 1a,b and their size scales with the dimension of the substituent(s). Figure 1c-f shows a clean Cu(111) surface and islands of the parasubstituted molecules. Fourier transformation (FT) ...

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Chemisorption and physisorption of alkanethiols on Cu(). A quantum mechanical investigation

Cited by 49 publications

References 77 publications

Reactivity of 1,8-octanedithiol monolayers on Au(111): Experimental and theoretical investigation

Reactivity of 1,8-octanedithiol monolayers on Au(111): Experimental and theoretical investigation

Methylthiolate adsorption on Au(111): Energetics, vibrational modes and STM imaging

Effect of Halo Substitution on the Geometry of Arenethiol Films on Cu(111)

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