Interface dipoles of organic molecules on Ag(111) in hybrid density-functional theory

Abstract

We investigate the molecular acceptors 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA), 2,3,5,6-tetra uoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), and 4,5,9,10-pyrenetetraone (PYTON) on Ag(111) using densityfunctional theory. For two groups of the HSE(α, ω) family of exchange-correlation functionals (ω= 0 and ω= 0.2Å) we study the isolated components as well as the combined systems as a function of the amount of exact-exchange (α). We find that hybrid functionals favour electron transfer to the adsorbate. Comparing to experimental work-function data, we report for (α) ca. 0.25 a notable but small improvement over (semi)local functionals for the interface dipole. Although Kohn-Sham eigenvalues are only approximate representations of ionization energies, incidentally, at this value also the density of states agrees well with the photoelectron spectra. However, increasing (α) to values for which the energy of the lowest unoccupied molecular orbital matches the experimental electron affinity in the gas phase worsens both the interface dipole and the density of states. Our results imply that semi-local DFT calculations may often be adequate for conjugated organic molecules on metal surfaces and that the much more computationally demanding hybrid functionals yield only small improvements.

submitted to New Journal of Physics (2013). More information can be found at http://th.fhi-berlin.mpg.de/site/index.php?n=Publications.Publications

References in corpus (12)

• Renormalization of Molecular Electronic Levels at Metal-Molecule Interfaces
• Quasiparticle band structure based on a generalized Kohn-Sham scheme
• Koopmans' condition for density-functional theory
• Dipole formation at metal/PTCDA interfaces: Role of the Charge Neutrality Level
• A Benchmark of GW Methods for Azabenzenes: Is the GW Approximation Good Enough?
• Renormalization of Molecular Quasiparticle Levels at Metal-Molecule Interfaces: Trends Across Binding Regimes
• Long-range-corrected hybrids including RPA correlation
• Piecewise Linearity of Approximate Density Functionals Revisited: Implications for Frontier Orbital Energies
• Relating Energy Level Alignment and Amine-Linked Single Molecule Junction Conductance
• Level alignment of a prototypical photocatalytic system: Methanol on TiO2(110)
• Quantitative analysis of valence photoemission spectra and quasiparticle excitations at chromophore-semiconductor interfaces
• Surface dipole of F4TCNQ films: Collective charge transfer and dipole-dipole repulsion in submonolayers

Cited by in corpus (16)

• Fundamental gaps with approximate density functionals: the derivative discontinuity revealed from ensemble considerations
• Energy Level Alignment at Molecule-Metal Interfaces from an Optimally-Tuned Range-Separated Hybrid Functional
• Orbital tomography of hybridized and dispersing molecular overlayers
• Binding and Electronic Level Alignment of $\mathbf{\pi }$-Conjugated Systems on Metals
• First-Principles Description of Charge Transfer in Donor-Acceptor Compounds from Self-Consistent Many-Body Perturbation Theory
• Detecting stable adsorbates of (1S)-camphor on Cu(111) with Bayesian optimization
• Surface Self-Assembly of Functionalized Molecules on Ag(111): More Than Just Chemical Intuition
• Interfacial charge rearrangement and intermolecular interactions: Density-functional theory study of free-base porphine adsorbed on Ag(111) and Cu(111)
• Leaving the Valley: Charting the Energy Landscape of Metal/Organic Interfaces via Machine Learning
• Reproducibility of Potential Energy Surfaces of Organic/Metal Interfaces on the Example of PTCDA on Ag(111)
• Symmetry, Shape and Energy Variations in Frontier Molecular Orbitals at Organic/Metal Interfaces: the Case of F${}_4$TCNQ
• How much does surface polymorphism influence the work function of organic/metal interfaces?
• Can we predict interface dipoles based on molecular properties?
• A many-body perturbation theory approach to energy band alignment at the crystalline tetracene-silicon interface
• Vertical bonding distances and interfacial band structure of PTCDA on a Sn-Ag surface alloy
• Förster-induced energy transfer in functionalized graphene