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Molecule-metal interfaces have a broad range of applications in nanoscale materials science. Accurate characterization of their electronic structures from first-principles is key in understanding material and device properties. The GW approach within many-body perturbation theory is state-of-the-art and can in principle yield accurate quasiparticle energy levels and interfacial level alignments that are in quantitative agreement with experiments. However, the interfaces are large heterogeneous systems that are currently challenging for first-principles GW calculations. In this work, we develop a GW-based dielectric embedding approach for molecule-metal interfaces, significantly reducing the computational cost of direct GW without sacrificing accuracy. To be specific, we perform explicit GW calculations only in the simulation cell of the molecular adsorbate, in which the dielectric effect of the metallic substrate is embedded. This is made possible via a real-space truncation of the substrate polarizability and the use of the interface plasma frequency in the adsorbate GW calculation. Here, we focus on the level alignment at weakly coupled molecule-metal interfaces, i.e., the energy difference between a molecular frontier orbital resonance and the substrate Fermi level. We demonstrate our method and assess a few GW-based approximations using two well-studied systems, benzene adsorbed on the Al (111) and on the graphite (0001) surfaces., Comment: 8 pages, 2 figures

We combine a GW approach and ab initio Molecular Dynamics (AIMD) simulations to study the impact of thermal effects on transport gap in solid pentacene (C22H14). The dynamic disorder induced by thermal fluctuations is simulated by AIMD, providing the ensemble-averaged density of states (DOS) near the band gap. The GW corrected DOS, averaged over hundreds of snapshots from AIMD simulation containing disordered structures indicates that the edge-to-edge transport gap is 2.1+/-0.04 eV, reduced by ~0.1 eV in contrast to the static 0 K GW calculation. The peak-to-peak gap is found to be 2.7eV in excellent agreement with experiment after corrections for the surface and the Frank-Condon effects and providing fully ab initio agreement with experiment where previous theory required ad hoc Gaussian broadening and temperature corrections.

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, 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., Comment: 15 pages, 8 figures

Above the Kondo temperature, the Kohn-Sham zero-bias conductance of an Anderson junction has been shown to completely miss the Coulomb blockade. Within a standard model for the spectral function, we deduce a parameterization for both the onsite exchange-correlation potential and the bias drop as a function of the site occupation that applies for all correlation strengths. We use our results to sow doubt on the common interpretation of such corrections as arising from dynamical exchange-correlation contributions., Comment: 9 pages, 8 figures, submitted to Phys. Rev. B

The electronic structure of organic-inorganic interfaces often feature resonances originating from discrete molecular orbitals coupled to continuum lead states. An example are molecular junctions, individual molecules bridging electrodes, where the shape and peak energy of such resonances dictate junction conductance, thermopower, I-V characteristics and related transport properties. In molecular junctions where off-resonance coherent tunneling dominates transport, resonance peaks in the transmission function are often assumed to be Lorentzian functions with an energy-independent broadening parameter $\Gamma$. Here we define a new energy-dependent resonance broadening function, $\Gamma(E)$, based on diagonalization of non-Hermitian matrices, which can describe resonances of a more complex, non-Lorentzian nature and can be decomposed into components associated with the left and right lead, respectively. We compute this quantity via an \emph{ab initio} non-equilibrium Green's function approach based on density functional theory for both symmetric and asymmetric molecular junctions, and show that our definition of $\Gamma(E)$, when combined with Breit-Wigner formula, reproduces the transmission calculated from DFT-NEGF. Through a series of examples, we illustrate how this approach can shed new light on experiments and understanding of junction transport properties in terms of molecular orbitals., Comment: 6 pages, 5 figures, submitted to J. Chem. Phys

The exact ground-state exchange-correlation functional of Kohn-Sham density functional theory yields the exact transmission through an Anderson junction at zero bias and temperature. The exact impurity charge susceptibility is used to construct the exact exchange-correlation potential. We analyze the successes and limitations of various types of approximations, including smooth and discontinuous functionals of the occupation, as well as symmetry-broken approaches., Comment: 6 pages, 5 figures, submitted to Phys. Rev. B

Transport through an Anderson junction (two macroscopic electrodes coupled to an Anderson impurity) is dominated by a Kondo peak in the spectral function at zero temperature. The exact single-particle Kohn-Sham potential of density functional theory reproduces the linear transport exactly, despite the lack of a Kondo peak in its spectral function. Using Bethe ansatz techniques, we calculate this potential exactly for all coupling strengths, including the cross-over from mean-field behavior to charge quantization caused by the derivative discontinuity. A simple and accurate interpolation formula is also given., Comment: 5 pages, 4 figures

Modern density functional theory (DFT) calculations employ the Kohn-Sham (KS) system of non-interacting electrons as a reference, with all complications buried in the exchange-correlation energy (Exc). The adiabatic connection formula gives an exact expression for Exc. We consider DFT calculations that instead employ a reference of strictly-correlated electrons. We define a "decorrelation energy" that relates this reference to the real system, and derive the corresponding adiabatic connection formula. We illustrate this theory in three situations, namely the uniform electron gas, Hooke's atom, and the stretched hydrogen molecule. The adiabatic connection for strictly-correlated electrons provides an alternative perspective for understanding density functional theory and constructing approximate functionals., Comment: 4 figures, has been published in J. Chem. Phys

In density functional theory (DFT), the exchange-correlation functional can be exactly expressed by the adiabatic connection integral. It has been noticed that as lambda goes to infinity, the lambda^(-1) term in the expansion of W(lambda) vanishes. We provide a simple but rigorous derivation to this exact condition in this work. We propose a simple parametric form for the integrand, satisfying this condition, and show that it is highly accurate for weakly-correlated two-electron systems., Comment: 4 pages, 2 figures, submitted to Phys. Rev. A