Adsorption of Benzene on Coinage Metals:  A Theoretical Analysis Using Wavefunction-Based Methods

Caputo, Riccarda; Prascher, Brian P.; Staemmler, Volker; Bagus, Paul S.; Wöll, Christof

doi:10.1021/jp076339q

Cited by 41 publications

(54 citation statements)

References 54 publications

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“…4 shows that dispersive interactions are indeed important in benzene adsorption on Au(111). The calculated adsorption distance of 3.7 Å is similar to those found in MP2 calculations for benzene on the (111) surfaces of Au, Ag and Cu [15] and to DFT calculations using the vdW-DF of benzene adsorption on graphene [24] and on the basal plane of MoS 2 [18].…”

Section: Resultssupporting

confidence: 77%

“…In recent MP2 calculations benzene adsorption on the (111) surfaces of Cu, Ag, and Au was considered [15]. The calculated adsorption energy for the Au(111) surface of -0.31 eV at an equilibrium benzenemetal distance of 3.6 Å was somewhat weaker than the experimental value of -0.6 eV reported in the same study.…”

Section: Introductionmentioning

confidence: 65%

“…Experimental [4,6] and theoretical [14] studies have shown that the non-planar distortions of the benzene molecule upon adsorption on Au(111) are negligible. The van der Waals interaction responsible for physisorption is not expected to depend significantly on the adsorption geometry and theoretical studies of benzene adsorption on coinage metals often consider this completely planar benzene geometry in the on-top adsorption site [15,27,28]. Defining the benzene-Au(111) separation as the distance between the center of the aromatic ring and the top-layer Au atom residing exactly beneath the center of the C 6 ring unambiguously defines the molecule-surface distance.…”

Section: Methodsmentioning

confidence: 99%

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RPBE-vdW Description of Benzene Adsorption on Au(111)

et al. 2010

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Density functional theory has become a popular methodology for the analysis of molecular adsorption on surfaces. Despite this popularity, there exist adsorption systems for which commonly used exchange-correlation functionals fail miserably. Particularly those systems where binding is due to van der Waals interactions. The adsorption of benzene on Au (111) is an often mentioned such system where standard density functionals predict a very weak adsorption or even a repulsion, whereas a significant adsorption is observed experimentally. We show that a considerable improvement in the description of the adsorption of benzene on Au(111) is obtained when using the so-called RPBE-vdW functional.

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Section: Resultssupporting

confidence: 77%

Section: Introductionmentioning

confidence: 65%

Section: Methodsmentioning

confidence: 99%

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RPBE-vdW Description of Benzene Adsorption on Au(111)

et al. 2010

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“…These results are consistent with the general understanding that the stronger the coupling, the more severe is the perturbation of the intrinsic molecular states. As the adsorption of benzene on Cu(111) has been well documented [25][26][27][28][29][30], here we attempt to understand our results using benzene as a reference. Benzene is weakly adsorbed with an adsorption height of 3:6 $ 3:7 A [27,29,30].…”

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confidence: 99%

Cooperative Modulation of Electronic Structures of Aromatic Molecules Coupled to Multiple Metal Contacts

et al. 2013

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We use cryogenic scanning tunneling microscopy and spectroscopy and density-functional theory calculations to inspect the modulation of electronic states of aromatic molecules. The molecules are selfassembled on a Cu(111) surface forming molecular networks in which the molecules are in different contact configurations, including laterally coupled to different numbers of coordination bonds and vertically adsorbed at different heights above the substrate. We quantitatively analyze the molecular states and find that a delocalized empty molecular state is modulated by these multiple contacts in a cooperative manner: its energy is down shifted by $0:16 eV for each additional lateral contact and by $0:1 eV as the vertical molecule-surface distance is reduced by 0.1 Å in the physisorption regime. We also report that in a moleculemetal-molecule system the bridging metal can mediate the electronic states of the two molecules. DOI: 10.1103/PhysRevLett.110.046802 PACS numbers: 73.20.Hb, 68.37.Ef, 73.63.Rt, 85.65.+h The electronic structure of a molecule is subject to the coupling of the molecule with its environment [1,2]. A thorough understanding of this issue is of great importance in the field of molecular electronics considering that the characteristics of molecular devices are determined by the molecular electronic structures and their contacts [3]. For example, a metal-molecule interface may strongly modify the molecular orbitals, and consequently, molecular conductance [3]. As one of the ultimate goals of molecular electronics is to realize single-molecule devices, wherein single molecules are connected to electrodes, one needs to understand how molecule-electrode coupling affects the molecular electronic structures at the level of individual molecules. Scanning tunneling microscopy and spectroscopy (STM-STS) have been used to address this challenging problem owing to their capability of resolving geometric details of molecule-metal contacts and simultaneously measuring the single-molecule electronic properties. These studies revealed in great detail that the molecular frontier orbitals are modulated when the molecules are coupled to metal atoms or a metal substrate [4][5][6][7][8][9][10][11][12][13][14]. So far, most of these studies focused on molecules coupled to one or at most two metal contacts. In future single-molecule devices, however, the molecules will be mostly connected to multiple electrodes, for example, to source, drain and gate electrodes in a field-effect transistor [15][16][17][18][19][20]. It is highly desirable to study individual molecules that are coupled to multiple metal contacts.In this Letter, we report on a combined study with low-temperature STM-STS and density-functional theory (DFT) of the electronic structures of extended aromatic molecules that are coupled with multiple metal contacts. The molecules are attached laterally to two or three neighboring molecules through metal-ligand coordination bonds and vertically to a metal surface at different distance. These parameters can be se...

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“…recent findings for graphene adsorption 48 ). Experimental results for Ni, 28 Cu, 29,30 Ag, 31,32 and Au 33 are indicated by crosses. Bond lengths are measured from the carbon ring to the closest metal atom, inÅ, and listed to signal chemisorption (short) and physisorption (long).…”

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confidence: 99%