Electronic and superconducting properties of silicon and carbon clathrates

We review the electronic properties of pure and doped silicon and carbon clathrates. Using accurate quasiparticle calculations within the GW approximation, we show that undoped clathrates are similar to 1.8 eV band gap semiconducting compounds. Further, the effect of doping by elements more electronegative than Si is shown to lead to p-type doped semiconductors with a similar to2.3-2.5 eV band gap in the visible energy range. Similar results are observed under doping of hydrogenated Si(n) (n = 20, 24, 28) clusters and rationalized on the basis of group theory analysis. Finally, the superconducting properties of doped clathrates are discussed. We show that superconductivity is an intrinsic property of the standard silicon sp(3) environment provided that efficient doping can be achieved. (C) 2003 Published by Elsevier B.V

Resonant hot charge-transfer excitations in fullerene-porphyrin complexes: a many-body Bethe-Salpeter study

We study within the many-body Green's function GW and Bethe-Salpeter approaches the neutral singlet excitations of the zinctetraphenylporphyrin and C70 fullerene donor-acceptor complex. The lowest transition is a charge-transfer excitation between the donor and the acceptor with an energy in excellent agreement with recent constrained density functional theory calculations. Beyond the lowest charge-transfer state, of which the energy can be determined with simple electrostatic models that we validate, the Bethe-Salpeter approach provides the full excitation spectrum. We evidence the existence of hot electron-hole states which are resonant in energy with the lowest donor intramolecular excitation and show an hybrid intramolecular and charge-transfer character, favouring the transition towards charge separation. These findings support the recently proposed scenario for charge separation at donor-acceptor interfaces through delocalized hot charge-transfer states.Comment: 9 pages, 4 figure

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

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

Tailoring band gap and hardness by intercalation: An ab initio study of I-8@Si-46 and related doped clathrates

We present an ab initio study of the structural and electronic properties of the recently synthesized I-8@Si-46 clathrate which is shown to be a degenerate p-type doped system. The intercalation significantly opens the band gap to a 1.75 eV value within the density functional theory. We study further the intercalation by other neighboring elements. A quasiparticle study reveals that such systems can display a band gap in the ``green-light'' energy range. Finally, we show that the bulk modulus can be increased to values equivalent to the one of the diamond phase

Many-body Green's function GW and Bethe-Salpeter study of the optical excitations in a paradigmatic model dipeptide

We study within the many-body Green's function GW and Bethe-Salpeter formalisms the excitation energies of a paradigmatic model dipeptide, focusing on the four lowest-lying local and charge-transfer excitations. Our GW calculations are performed at the self-consistent level, updating first the quasiparticle energies, and further the single-particle wavefunctions within the static Coulomb-hole plus screened-exchange approximation to the GW self-energy operator. Important level crossings, as compared to the starting Kohn-Sham LDA spectrum, are identified. Our final Bethe-Salpeter singlet excitation energies are found to agree, within 0.07 eV, with CASPT2 reference data, except for one charge-transfer state where the discrepancy can be as large as 0.5 eV. Our results agree best with LC-BLYP and CAM-B3LYP calculations with enhanced long-range exchange, with a 0.1 eV mean absolute error. This has been achieved employing a parameter-free formalism applicable to metallic or insulating extended or finite systems.Comment: 25 pages, 5 figure

Dynamical Correction to the Bethe-Salpeter Equation Beyond the Plasmon-Pole Approximation

The Bethe-Salpeter equation (BSE) formalism is a computationally affordable method for the calculation of accurate optical excitation energies in molecular systems. Similar to the ubiquitous adiabatic approximation of time-dependent density-functional theory, the static approximation, which substitutes a dynamical (i.e., frequency-dependent) kernel by its static limit, is usually enforced in most implementations of the BSE formalism. Here, going beyond the static approximation, we compute the dynamical correction of the electron-hole screening for molecular excitation energies thanks to a renormalized first-order perturbative correction to the static BSE excitation energies. The present dynamical correction goes beyond the plasmon-pole approximation as the dynamical screening of the Coulomb interaction is computed exactly within the random-phase approximation. Our calculations are benchmarked against high-level (coupled-cluster) calculations, allowing to assess the clear improvement brought by the dynamical correction for both singlet and triplet optical transitions.Comment: 12 pages, 2 figure

Static versus dynamically polarizable environments within the many-body GW\bf{GW} formalism

Continuum or discrete polarizable models for the study of optoelectronic processes in embedded subsystems rely mostly on the restriction of the surrounding electronic dielectric response to its low frequency limit. Such a description hinges on the assumption that the electrons in the surrounding medium react instantaneously to any excitation in the central subsystem, treating thus the environment in the adiabatic limit. Exploiting a recently developed embedded $GW$ formalism, with an environment described at the fully ab initio level, we assess the merits of the adiabatic limit with respect to an environment where the full dynamics of the dielectric response is considered. Further, we show how to properly take the static limit of the environment susceptibility, introducing the so-called Coulomb-hole and screened-exchange contributions to the reaction field. As a first application, we consider a C$_{60}$ molecule at the surface of a C$_{60}$ crystal, namely a case where the dynamics of the embedded and embedding subsystems are similar. The common adiabatic assumption, when properly treated, generates errors below $10\%$ on the polarization energy associated with frontier energy levels and associated energy gaps. Finally, we consider a water molecule inside a metallic nanotube, the worst case for the environment adiabatic limit. The error on the gap polarization energy remains below $10\%$, even though the error on the frontier orbitals polarization energies can reach a few tenths of an electronvolt

Many-body GWGW calculations with very large scale polarizable environments made affordable: a fully ab initio QM/QM approach

We present a many-body $GW$ formalism for quantum subsystems embedded in discrete polarizable environments containing up to several hundred thousand atoms described at a fully ab initio random phase approximation level. Our approach is based on a fragment approximation in the construction of the Green's function and independent-electron susceptibilities. Further, the environing fragments susceptibility matrices are reduced to a minimal but accurate representation preserving low order polarizability tensors through a constrained minimization scheme. This approach dramatically reduces the cost associated with inverting the Dyson equation for the screened Coulomb potential $W$, while preserving the description of short to long-range screening effects. The efficiency and accuracy of the present scheme is exemplified in the paradigmatic cases of fullerene bulk, surface, subsurface, and slabs with varying number of layers

Ab initio many-body GW correlations in the electronic structure of LaNiO2_2

We present an ab initio $GW$ self-energy calculation of the electronic structure of LaNiO$_2$. With respect to density-functional theory we find that in $GW$ the La 4$f$ states undergo an important $+$2 eV upward shift from the Fermi level, while the O 2$p$ states are pulled down by $-$1.5 eV, thus reinforcing the charge-transfer character of this material. However, $GW$ many-body effects leave the $d$-like bands at the Fermi level almost unaffected, so that the Fermi-surface topology is preserved, unlike in cuprates.Comment: 6 pages, 6 figures, 2 table