First-principles study of benzene on noble metal surfaces: Adsorption states and vacuum level shifts

Toyoda, Kenji; Nakano, Yukiko; Hamada, Ikutaro; Lee, Kyuho; Yanagisawa, Susumu; Morikawa, Yoshitada

doi:10.1016/j.susc.2009.07.039

Cited by 90 publications

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“…Benzene is weakly adsorbed with an adsorption height of 3:6 $ 3:7 A [27,29,30]. Toyoda et al predicted that a reduction of the benzeneCu distance lowers the work function at a rate of $0:1 eV=0:1 A when the distance falls in the range of 2.5-3.5 Å [29]. Our data allow us to test this prediction since the energy position of the STS resolved states depends on the effective work function.…”

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confidence: 55%

“…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%

“…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]. Toyoda et al predicted that a reduction of the benzeneCu distance lowers the work function at a rate of $0:1 eV=0:1 A when the distance falls in the range of 2.5-3.5 Å [29].…”

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

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“…15 These work functions can then be additionally tuned by noncovalent adsorption of organic molecules on the metallic surface in hybrid organic−inorganic interfaces. 15,303,316 …”

Section: Structural and Electronic Propertiesmentioning

confidence: 99%

First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications

2017

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Noncovalent van der Waals (vdW) or dispersion forces are ubiquitous in nature and influence the structure, stability, dynamics, and function of molecules and materials throughout chemistry, biology, physics, and materials science. These forces are quantum mechanical in origin and arise from electrostatic interactions between fluctuations in the electronic charge density. Here, we explore the conceptual and mathematical ingredients required for an exact treatment of vdW interactions, and present a systematic and unified framework for classifying the current first-principles vdW methods based on the adiabatic-connection fluctuation−dissipation (ACFD) theorem (namely the Rutgers−Chalmers vdW-DF, Vydrov−Van Voorhis (VV), exchange-hole dipole moment (XDM), Tkatchenko−Scheffler (TS), many-body dispersion (MBD), and random-phase approximation (RPA) approaches). Particular attention is paid to the intriguing nature of many-body vdW interactions, whose fundamental relevance has recently been highlighted in several landmark experiments. The performance of these models in predicting binding energetics as well as structural, electronic, and thermodynamic properties is connected with the theoretical concepts and provides a numerical summary of the state-of-the-art in the field. We conclude with a roadmap of the conceptual, methodological, practical, and numerical challenges that remain in obtaining a universally applicable and truly predictive vdW method for realistic molecular systems and materials.

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“…[1][2][3] These ultimately evolved into the van der Waals density functional ͑vdW-DF͒ for arbitrary geometries. [4][5][6] Despite its success for describing dispersion in a breadth of systems better than any other nonempirical method, 7 vdW-DF overestimates equilibrium separations 4,5,[7][8][9][10][11][12] and underestimates hydrogen-bond strength. 13,14 In this Rapid Communication, we propose a second version of the van der Waals density functional ͑vdW-DF2͒ employing a more accurate semilocal exchange functional PW86 ͑Refs.…”

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Higher-accuracy van der Waals density functional

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First-principles study of benzene on noble metal surfaces: Adsorption states and vacuum level shifts

Cited by 90 publications

References 50 publications

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

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

First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications

Higher-accuracy van der Waals density functional

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