Energy level alignment of self-assembled linear chains of benzenediamine on Au(111) from first principles

Guo, Li; Rangel, Tonatiuh; Liu, Zhen Fei; Cooper, Valentino R.; Neaton, Jeffrey B.

doi:10.1103/physrevb.93.125429

Cited by 9 publications

(22 citation statements)

References 54 publications

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“…Importantly, the DFT + Σ calculations in Ref. 125 only rigidly shift the PBE PDOS, leaving the lineshape unchanged, in contrast to our OT-RSH approach with its inherent self-consistency when solving the GKS equation. Accordingly, in Fig.…”

Section: Bda On Au(111)mentioning

confidence: 99%

“…BDA adsorbed on Au(111) has attracted considerable attention in both experimental 19,123 and theoretical 36,79,124,125 studies. However, the adsorption geometry has only been revealed recently with scanning tunneling microscopy measurements, 123 which suggest that BDA molecules form selfassembled linear chains on Au (111).…”

Section: Bda On Au(111)mentioning

confidence: 99%

“…We note in passing that for the purpose of tuning β, we directly take the intermolecular polarization of 0.3 eV from Ref. 125, without attempting to determine this value from DFT or from classical electrostatic calculations (see Refs. 90 and 126-129 for such examples).…”

Section: Bda On Au(111)mentioning

confidence: 99%

“…Here, we use the same geometry as in Ref. 125 but calculate the PDOS of the interface self-consistently with our new OT-RSH approach. We use 3 layers of Au (111) as the substrate and a 4×6×1 k-mesh (2 ×3×1 for the Fock exchange contribution).…”

Section: Bda On Au(111)mentioning

confidence: 99%

“…36 In Ref. 125, standard DFT + Σ calculations were performed to correct the PBE PDOS, without altering the PDOS lineshape. Here, we use the same geometry as in Ref.…”

Section: Bda On Au(111)mentioning

confidence: 99%

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Energy level alignment at molecule-metal interfaces from an optimally tuned range-separated hybrid functional

Liu

Egger

Refaely-Abramson

et al. 2017

The Journal of Chemical Physics

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The alignment of the frontier orbital energies of an adsorbed molecule with the substrate Fermi level at metal-organic interfaces is a fundamental observable of significant practical importance in nanoscience and beyond. Typical density functional theory calculations, especially those using local and semi-local functionals, often underestimate level alignment leading to inaccurate electronic structure and charge transport properties. In this work, we develop a new fully self-consistent predictive scheme to accurately compute level alignment at certain classes of complex heterogeneous molecule-metal interfaces based on optimally tuned range-separated hybrid functionals. Starting from a highly accurate description of the gas-phase electronic structure, our method by construction captures important nonlocal surface polarization effects via tuning of the long-range screened exchange in a range-separated hybrid in a non-empirical and system-specific manner. We implement this functional in a plane-wave code and apply it to several physisorbed and chemisorbed molecule-metal interface systems. Our results are in quantitative agreement with experiments, for both the level alignment and work function changes. Our approach constitutes a new practical scheme for accurate and efficient calculations of the electronic structure of molecule-metal interfaces.

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Section: Bda On Au(111)mentioning

confidence: 99%

Section: Bda On Au(111)mentioning

confidence: 99%

Section: Bda On Au(111)mentioning

confidence: 99%

Section: Bda On Au(111)mentioning

confidence: 99%

“…36 In Ref. 125, standard DFT + Σ calculations were performed to correct the PBE PDOS, without altering the PDOS lineshape. Here, we use the same geometry as in Ref.…”

Section: Bda On Au(111)mentioning

confidence: 99%

See 3 more Smart Citations

Energy level alignment at molecule-metal interfaces from an optimally tuned range-separated hybrid functional

Liu

Egger

Refaely-Abramson

et al. 2017

The Journal of Chemical Physics

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Calculation of Energy Level Alignment and Interface Electronic Structure in Molecular Junctions beyond DFT

Montes

Vázquez

2021

J. Phys. Chem. C

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In atomistic simulations of molecular junctions, it is important to develop methods beyond density-functional theory (DFT) to describe the interface electronic structure and alignment of frontier molecular orbitals accurately. Here we describe a first-principles approach for molecular junctions that extends the DFT+Σ method, an approximate scheme based on self-energy corrections. The DFT+Σtot method presented here acts on junction states and introduces corrections to DFT-based molecular frontier orbitals not only on the molecular subspace but on the whole junction Hamiltonian. These self-energy corrections are scaled according to the molecular character of each junction wave function, a character which is given by projection coefficients between molecular orbitals and junction states. We illustrate this formalism in three paradigmatic weakly interacting single molecule junctions. Despite the weak metal/molecule interaction, calculated projection coefficients show metal/molecule hybridization resulting in molecular orbital features that can be significantly broadened over a wide energy range. Scaling of self-energy corrections to molecular levels seamlessly accounts for this hybridization and spectral delocalization. The resulting DFT+Σtot electronic structure brings molecular frontier orbital energies to values comparable to the G0W0 and WKM approaches. By considering the whole spectral distribution of molecular orbitals, DFT+Σtot shifts not just the main molecular peaks but modifies the whole junction electronic structure.

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Energy Level Alignment at Hybridized Organic–Metal Interfaces: The Role of Many-Electron Effects

2017

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Hybridized molecule/metal interfaces are ubiquitous in molecular and organic devices. The energy level alignment (ELA) of frontier molecular levels relative to the metal Fermi level (EF) is critical to the conductance and functionality of these devices. However, a clear understanding of the ELA that includes many-electron self-energy effects is lacking. Here, we investigate the many-electron effects on the ELA using state-of-the-art, benchmark GW calculations on prototypical chemisorbed molecules on Au(111), in eleven different geometries. The GW ELA is in good agreement with photoemission for monolayers of benzene diamine on Au(111). We find that in addition to static image charge screening, the frontier levels in most of these geometries are renormalized by additional screening from substrate-mediated intermolecular Coulomb interactions. For weakly chemisorbed systems, such as amines and pyridines on Au, this additional level renormalization (∼1.5 eV) comes solely from static screened exchange energy, allowing us to suggest computationally more tractable schemes to predict the ELA at such interfaces. However, for more strongly chemisorbed thiolate layers, dynamical effects are present. Our ab initio results constitute an important step toward the understanding and manipulation of functional molecular/organic systems for both fundamental studies and applications.3

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Energy level alignment of self-assembled linear chains of benzenediamine on Au(111) from first principles

Cited by 9 publications

References 54 publications

Energy level alignment at molecule-metal interfaces from an optimally tuned range-separated hybrid functional

Energy level alignment at molecule-metal interfaces from an optimally tuned range-separated hybrid functional

Calculation of Energy Level Alignment and Interface Electronic Structure in Molecular Junctions beyond DFT

Energy Level Alignment at Hybridized Organic–Metal Interfaces: The Role of Many-Electron Effects

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