Ab initio calculations of response properties including electron-hole interaction

We discuss the current status of a computational approach which allows to evaluate the dielectric matrix, and hence electronic excitations like optical properties, including local field and excitonic effects. We introduce a recent numerical development which greatly reduces the use of memory in such type of calculations, and hence eliminates one of the bottlenecks for the application to complex systems. We present recent applications of the method, focusing our interest on insulating oxides.Comment: 11 pages, 5 figures, 1999 MRS Proceedin

First-principles GW calculations for fullerenes, porphyrins, phtalocyanine, and other molecules of interest for organic photovoltaic applications

We evaluate the performances of ab initio GW calculations for the ionization energies and HOMO-LUMO gaps of thirteen gas phase molecules of interest for organic electronic and photovoltaic applications, including the C60 fullerene, pentacene, free-base porphyrins and phtalocyanine, PTCDA, and standard monomers such as thiophene, fluorene, benzothiazole or thiadiazole. Standard G0W0 calculations, that is starting from eigenstates obtained with local or semilocal functionals, significantly improve the ionization energy and band gap as compared to density functional theory Kohn-Sham results, but the calculated quasiparticle values remain too small as a result of overscreening. Starting from Hartree-Fock-like eigenvalues provides much better results and is equivalent to performing self-consistency on the eigenvalues, with a resulting accuracy of 2~4% as compared to experiment. Our calculations are based on an efficient gaussian-basis implementation of GW with explicit treatment of the dynamical screening through contour deformation techniques.Comment: 10 pages, 3 figure

Can molecular projected density-of-states (PDOS) be systematically used in electronic conductance analysis?

Using benzene-diamine and benzene-dithiol molecular junctions as benchmarks, we investigate the widespread analysis of the quantum transport conductance $\mathcal{G}(\epsilon)$ in terms of the projected density of states (PDOS) onto molecular orbitals (MOs). We first consider two different methods for identifying the relevant MOs: 1) diagonalization of the Hamiltonian of the isolated molecule, and 2) diagonalization of a submatrix of the junction Hamiltonian constructed by considering only basis elements localized on the molecule. We find that these two methods can lead to substantially different MOs and hence PDOS. Furthermore, within Method 1, the PDOS can differ depending on the isolated molecule chosen to represent the molecular junction (e.g. benzene-dithiol or -dithiolate); and, within Method 2, the PDOS depends on the chosen basis set. We show that these differences can be critical when the PDOS is used to provide a physical interpretation of the conductance (especially, when it has small values as it happens typically at zero bias). In this work, we propose a new approach trying to reconcile the two traditional methods. Though some improvements are achieved, the main problems are still unsolved. Our results raise more general questions and doubts on a PDOS-based analysis of the conductance.Comment: 12 pages, 9 figure

Ground-state correlation energy of beryllium dimer by the Bethe-Salpeter equation

Since the '30s the interatomic potential of the beryllium dimer Be$_2$ has been both an experimental and a theoretical challenge. Calculating the ground-state correlation energy of Be$_2$ along its dissociation path is a difficult problem for theory. We present ab initio many-body perturbation theory calculations of the Be$_2$ interatomic potential using the GW approximation and the Bethe-Salpeter equation (BSE). The ground-state correlation energy is calculated by the trace formula with checks against the adiabatic-connection fluctuation-dissipation theorem formula. We show that inclusion of GW corrections already improves the energy even at the level of the random-phase approximation. At the level of the BSE on top of the GW approximation, our calculation is in surprising agreement with the most accurate theories and with experiment. It even reproduces an experimentally observed flattening of the interatomic potential due to a delicate correlations balance from a competition between covalent and van der Waals bonding.Comment: 6 pages, 2 figures, 1 tabl

Beyond time-dependent exact-exchange: the need for long-range correlation

In the description of the interaction between electrons beyond the classical Hartree picture, bare exchange often yields a leading contribution. Here we discuss its effect on optical spectra of solids, comparing three different frameworks: time-dependent Hartree-Fock, a recently introduced combined density-functional and Green's functions approach applied to the bare exchange self-energy, and time-dependent exact-exchange within time-dependent density-functional theory (TD-EXX). We show that these three approximations give rise to identical excitonic effects in solids; these effects are drastically overestimated for semiconductors. They are partially compensated by the usual overestimation of the quasiparticle band gap within Hartree-Fock. The physics that lacks in these approaches can be formulated as screening. We show that the introduction of screening in TD-EXX indeed leads to a formulation that is equivalent to previously proposed functionals derived from Many-Body Perturbation Theory. It can be simulated by reducing the long-range part of the Coulomb interaction: this produces absorption spectra of semiconductors in good agreement with experiment.Comment: 12 pages, 3 figures, 1 tabl

Many-body correlations and coupling in benzene-dithiol junctions

Most theoretical studies of nanoscale transport in molecular junctions rely on the combination of the Landauer formalism with Kohn-Sham density functional theory (DFT) using standard local and semilocal functionals to approximate exchange and correlation effects. In many cases, the resulting conductance is overestimated with respect to experiments. Recent works have demonstrated that this discrepancy may be reduced when including many-body corrections on top of DFT. Here we study benzene-dithiol (BDT) gold junctions and analyze the effect of many-body perturbation theory (MBPT) on the calculation of the conductance with respect to different bonding geometries. We find that the many-body corrections to the conductance strongly depend on the metal-molecule coupling strength. In the BDT junction with the lowest coupling, many-body corrections reduce the overestimation on the conductance to a factor two, improving the agreement with experiments. In contrast, in the strongest coupling cases, many-body corrections on the conductance are found to be sensibly smaller and standard DFT reveals a valid approach.Comment: 9 pages, 4 figure

Optical absorption in small BN and C nanotubes

We present a theoretical study of the optical absorption spectrum of small boron-nitride and carbon nanotubes using time-dependent density-functional theory and the random phase approximation. Both for C and BN tubes, the absorption of light polarized perpendicular to the tube-axis is strongly suppressed due to local field effects. Since BN-tubes are wide band-gap insulators, they only absorb in the ultra-violet energy regime, independently of chirality and diameter. In comparison with the spectra of the single C and BN-sheets, the tubes display additional fine-structure which stems from the (quasi-) one-dimensionality of the tubes and sensitively depends on the chirality and tube diameter. This fine structure can provide additional information for the assignment of tube indices in high resolution optical absorption spectroscopy.Comment: 5 pages, 3 figure

Ab initio GW many-body effects in graphene

We present an {\it ab initio} many-body GW calculation of the self-energy, the quasiparticle band plot and the spectral functions in free-standing undoped graphene. With respect to other approaches, we numerically take into account the full ionic and electronic structure of real graphene and we introduce electron-electron interaction and correlation effects from first principles. Both non-hermitian and also dynamical components of the self-energy are fully taken into account. With respect to DFT-LDA, the Fermi velocity is substantially renormalized and raised by a 17%, in better agreement with magnetotransport experiments. Furthermore, close to the Dirac point the linear dispersion is modified by the presence of a kink, as observed in ARPES experiments. Our calculations show that the kink is due to low-energy $\pi \to \pi^*$ single-particle excitations and to the $\pi$ plasmon. Finally, the GW self-energy does not open the band gap.Comment: 5 pages, 4 figures, 1 tabl

Transforming nonlocality into frequency dependence: a shortcut to spectroscopy

Measurable spectra are theoretically very often derived from complicated many-body Green's functions. In this way, one calculates much more information than actually needed. Here we present an in principle exact approach to construct effective potentials and kernels for the direct calculation of electronic spectra. In particular, the potential that yields the spectral function needed to describe photoemission turns out to be dynamical but {\it local} and {\it real}. As example we illustrate this ``photoemission potential'' for sodium and aluminium, modelled as homogeneous electron gas, and discuss in particular its frequency dependence stemming from the nonlocality of the corresponding self-energy. We also show that our approach leads to a very short derivation of a kernel that is known to well describe absorption and energy-loss spectra of a wide range of materials