Density-functional theory with screened van der Waals interactions applied to atomic and molecular adsorbates on close-packed and non-close-packed surfaces

Ruiz, Victor G.; Liu, Wei; Tkatchenko, Alexandre

doi:10.1103/physrevb.93.035118

Cited by 103 publications

(131 citation statements)

References 108 publications

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“…We note that, in popular pairwise vdW corrections, vdW coefficients of molecules on metal surfaces can be overestimated by as much as 500%, because these approaches miss the complex polarization effects in the extended surface that are typically responsible for reducing the vdW coefficients of atoms in metals by 50−500% with respect to the free-atom values. 76,77 The discrepancies in the vdW energy caused by small errors in asymptotic coefficients can lead to qualitatively incorrect conclusions about relative stabilities (not absolute energies) as well, such as when studying molecular crystal polymorphs. 78 In systems of increasing size, the binding arises from an interplay of short-and long-range interactions, so an accurate and reliable vdW method must be able to describe the binding at both equilibrium and asymptotic separations, as well as everything in-between, on equal footing.…”

Section: Conceptual Understanding Of Vdw Interactions In Molecules Anmentioning

confidence: 99%

“…Such renormalized bulk reference parameters can be used to investigate cohesion in solids 80,208 and adsorption of molecules on surfaces. 76,77,101,209 Furthermore, the TS approach was also extended from DFT 60 to the density-functional tight-binding (DFTB) method, 210 as well as classical force fields. 211,212 Sato and Nakai developed an atomic pairwise method that can be considered a direct bridge to the class of nonlocal functionals, by directly expanding an ALL-like density functional into a multipole series around the atomic centers.…”

Section: Chemical Reviewsmentioning

confidence: 99%

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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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Section: Conceptual Understanding Of Vdw Interactions In Molecules Anmentioning

confidence: 99%

Section: Chemical Reviewsmentioning

confidence: 99%

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

2017

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“…The studies above included the vdW force in the calculations, but neglected the pronounced contributions of many-body electronic correlations, which arise from the collective electronic fluctuations in the combined molecule/ surface system [25]. The vdW interactions have been shown to strongly affect the stability and structure of hybrid systems [26][27][28][29][30]. However, the most widely employed vdW-inclusive methods simply add a correction to the density-functional theory (DFT) total energy in the form of a non-local interaction energy [31,32].…”

Section: Introductionmentioning

confidence: 99%

Tuning the work function of stepped metal surfaces by adsorption of organic molecules

Jiang

et al. 2017

J. Phys.: Condens. Matter

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Understanding the binding mechanisms for aromatic molecules on transition-metal surfaces, especially with defects such as vacancies, steps and kinks, is a major challenge in designing functional interfaces for organic devices. One important parameter in the performance of organic/inorganic devices is the barrier of charge carrier injection. In the case of a metallic electrode, tuning the electronic interface potential or the work function for electronic level alignment is crucial. Here, we use density-functional theory (DFT) calculations with van der Waals (vdW) interactions treated with both screened pairwise (vdW surf ) and many-body dispersion (MBD) methods, to systematically study the interactions of benzene with a variety of stepped surfaces. Our calculations confirm the physisorptive character of Ag(2 1 1), Ag(5 3 3), Ag(3 2 2), Ag(7 5 5) and Ag(5 4 4) surfaces upon the adsorption of benzene. The MBD effects reduce the adsorption energies by about 0.15 eV per molecule compared to the results from the DFT + vdW surf method. In addition, we find that the higher the step density, the larger the reduction of the work function upon the adsorption of benzene. We also study the effect of vdW interactions on the electronic structure using a fully selfconsistent implementation of the vdW surf method in the Kohn-Sham DFT framework. We find that the self-consistent vdW surf effects increase the work function due to the lowered Fermi level and the increased vacuum level. As a result, the benzene/Ag(2 1 1) system has the lowest work function (3.67 eV) among the five adsorption systems, significantly smaller than the work function of the clean Ag(1 1 1) surface (4.74 eV). Our results provide important insights into the stability and electronic properties of molecules adsorbed on stepped metal surfaces, which could help in designing more appropriate interfaces with low work functions for electron transfer.

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“…While the first works with an additive pairwise potential, albeit with density-dependent coefficient, the second approach is able to take cooperative effects into account. Both the vdW surf and MBD methods have been shown to provide reliable adsorption energy and height for interfaces between organic molecules (such as benzene and PTCDA) and coinage metal surfaces [22][23][24] . Our results show that the inclusion of vdW corrections is crucial to correctly describe the flat adsorption geometry of anthracene on Ag(111); calculations using "pure" generalized gradient approximation (GGA), without including vdW corrections, resulted in a tilted configuration for anthracene/Ag(111), while the use of the vdW surf approach yielded flat molecular orientation, consistent with experimental observations.…”

Section: Introductionmentioning

confidence: 99%

The role of the van der Waals interactions in the adsorption of anthracene and pentacene on the Ag(111) surface

Morbec

Kratzer

2017

The Journal of Chemical Physics

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Using first-principles calculations based on density-functional theory (DFT) we investigated the effects of the van der Waals (vdW) interactions on the structural and electronic properties of anthracene and pentacene adsorbed on the Ag(111) surface. We found that the inclusion of vdW corrections strongly affects the binding of both anthracene/Ag(111) and pentacene/Ag(111), yielding adsorption heights and energies more consistent with the experimental results than standard DFT calculations with generalized gradient approximation (GGA). For anthracene/Ag(111) the effect of the vdW interactions is even more dramatic: we found that "pure" DFT-GGA calculations (without including vdW corrections) result in preference for a tilted configuration, in contrast to experimental observations of flat-lying adsorption; including vdW corrections, on the other hand, alters the binding geometry of anthracene/Ag(111), favoring the flat configuration. The electronic structure obtained using a self-consistent vdW scheme was found to be nearly indistinguishable from the conventional DFT electronic structure once the correct vdW geometry is employed for these physisorbed systems. Moreover, we show that a vdW correction scheme based on a hybrid functional DFT calculation (HSE) results in an improved description of the highest occupied molecular level of the adsorbed molecules.

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Density-functional theory with screened van der Waals interactions applied to atomic and molecular adsorbates on close-packed and non-close-packed surfaces

Cited by 103 publications

References 108 publications

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

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

Tuning the work function of stepped metal surfaces by adsorption of organic molecules

The role of the van der Waals interactions in the adsorption of anthracene and pentacene on the Ag(111) surface

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