Understanding the Metal–Molecule Interface from First Principles

Kronik, Leeor; Morikawa, Yoshitada

doi:10.1002/9783527653171.ch3

Cited by 16 publications

(18 citation statements)

References 144 publications

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“…The most common approach to the description of metal-ligand interphase is based on Density Functional Theory (DFT). The main challenge in predicting the electronic structure at the interphase from first principles consists in the selection of an approximate exchange-correlation density functional, able to accurately describe both sides of the interface [54]. Indeed, the presence of unexpected collective effects (charge transfer, polarization, interface-induced states, orbital hybridization) requires the introduction of hybrid functional, taking into account the contribution of the interface dipole.…”

Section: Chemical Bonding and Electronic Structure At The Metal-liganmentioning

confidence: 99%

Untangling the Role of the Capping Agent in Nanocatalysis: Recent Advances and Perspectives

et al. 2016

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Capping agents (organic ligands, polymers, surfactants, etc.) are a basic component in the synthesis of metal nanoparticles with controlled size and well-defined shape. However, their influence on the performances of nanoparticle-based catalysts is multifaceted and controversial. Indeed, capping agent can act as a "poison", limiting the accessibility of active sites, as well as a "promoter", producing improved yields and unpredicted selectivity control. These effects can be ascribed to the creation of a metal-ligand interphase, whose unique properties are responsible for the catalytic behavior. Therefore, understanding the structure of this interphase is of prime interest for the optimization of tailored nanocatalyst design. This review provides an overview of the interfacial key features affecting the catalytic performances and details a selection of related literature examples. Furthermore, we highlight critical points necessary for the design of highly selective and active catalysts with surface and interphase control.

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Section: Chemical Bonding and Electronic Structure At The Metal-liganmentioning

confidence: 99%

Untangling the Role of the Capping Agent in Nanocatalysis: Recent Advances and Perspectives

et al. 2016

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“…[9][10][11][12] Such investigations strongly benefit from accurate and com-putationally inexpensive theoretical models, which are often necessary for a better interpretation of experimental results. 13 An efficient work horse for first principles calculations of the electronic structure is density functional theory (DFT), 14,15 usually within the Kohn-Sham (KS) framework. 16,17 In this scheme, the original manyelectron problem is mapped uniquely into a fictitious noninteracting electron system, yielding the same electron density.…”

Section: Introductionmentioning

confidence: 99%

Experimental and theoretical electronic structure of quinacridone

et al. 2014

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The energy positions of frontier orbitals in organic electronic materials are often studied experimentally by (inverse) photoemission spectroscopy and theoretically within density functional theory. However, standard exchange-correlation functionals often result in too small fundamental gaps, may lead to wrong orbital energy ordering, and do not capture polarization-induced gap renormalization. Here, we examine these issues and a strategy for overcoming them by studying the gas phase and bulk electronic structure of the organic molecule quinacridone (5Q), a promising material with many interesting properties for organic devices. Experimentally, we perform angle-resolved photoemission spectroscopy (ARUPS) on thin films of the crystalline β-phase of 5Q. Theoretically, we employ an optimally-tuned range-separated hybrid functional (OT-RSH) within density functional theory. For the gas phase molecule, our OT-RSH result for the ionization potential (IP) represents a substantial improvement over the semi-local PBE and the PBE0 hybrid functional results, producing an IP in quantitative agreement with experiment. For the bulk crystal, we take into account the correct screening in the bulk, using the recently developed OT-SRSH approach, while retaining the optimally-tuned parameters for the range-separation and the short-range Fock exchange. This leads to a band gap narrowing due to polarization effects and results in a valence band spectrum in excellent agreement with experimental ARUPS data, with respect to both peak positions and heights. Finally, full-frequency G0W0 results based on a hybrid functional starting point are shown to agree with the OT-SRSH approach, improving substantially on the PBE-starting point.

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“…In terms of a simple barrier model, the band gap problem manifests as an underestimation of the potential barrier and hence an over-estimation of tunnelling transmission. A second difficulty facing many approximate DFT approaches in describing a MTJ is a poor description of image charge potentials for molecules absorbed at or bonded to metal surfaces [10]. An approach to overcome these shortcomings is to add self-energy corrections to the Kohn-Sham energy levels that compensate electron self-interactions and then to add corrections that also describe the image charge potential.…”

Section: Introductionmentioning

confidence: 99%

Electrode-molecule energy level offsets in a gold-benzene diamine-gold single molecule tunnel junction

Szepieniec

Greer

2020

The Journal of Chemical Physics

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One means for describing electron transport across single molecule tunnel junctions (MTJs) is to use density functional theory (DFT) in conjunction with a nonequilibrium Green's function (NEGF) formalism. This description relies on interpreting solutions to the Kohn-Sham (KS) equations used to solve the DFT problem as quasiparticle (QP) states. Many practical DFT implementations suffer from electron self-interaction errors and an inability to treat charge image potentials for molecules near metal surfaces. For MTJs, the overall effect of these errors is typically manifested as an overestimation of electronic currents. Correcting KS energies for self-interaction and image potential errors results in MTJ current-voltage characteristics in close agreement with measured currents. An alternative transport approach foregoes a QP picture and solves for a many-electron wavefunction on the MTJ subject to open system boundary conditions. It is demonstrated that this many-electron method provides similar results to the corrected QP picture for electronic current.Analysis of these two distinct approaches are related through corrections to a junction's electronic structure beyond the KS energies for the case of a benzene diamine molecule bonded between two gold electrodes.

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Understanding the Metal–Molecule Interface from First Principles

Cited by 16 publications

References 144 publications

Untangling the Role of the Capping Agent in Nanocatalysis: Recent Advances and Perspectives

Untangling the Role of the Capping Agent in Nanocatalysis: Recent Advances and Perspectives

Experimental and theoretical electronic structure of quinacridone

Electrode-molecule energy level offsets in a gold-benzene diamine-gold single molecule tunnel junction

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