P. Garcia-Gonzalez

First-Principles Description of Correlation Effects in Layered Materials

We present a first-principles description of anisotropic materials characterized by having both weak (dispersionlike) and strong covalent bonds, based on the adiabatic-connection fluctuation-dissipation theorem with density functional theory. For hexagonal boron nitride the in-plane and out-of-plane bonding as well as vibrational dynamics are well described both at equilibrium and when the layers are pulled apart. Bonding in covalent and ionic solids is also described. The formalism allows us to ping down the deficiencies of common exchange-correlation functionals and provides insight toward the inclusion of dispersion interactions into the correlation functional.

Ab initio nanoplasmonics: The impact of atomic structure

We present an ab-initio study of the hybridization of localized surface plasmons in a metal nanoparticle dimer. The atomic structure, which is often neglected in theoretical studies of quantum nanoplasmonics, has a strong impact on the optical absorption properties when sub-nanometric gaps between the nanoparticles are considered. We demonstrate that this influences the hybridization of optical resonances of the dimer, and leads to significantly smaller electric field enhancements as compared to the standard jellium model. In addition we show that the corrugation of the metal surface at a microscopic scale becomes as important as other well-known quantum corrections to the plasmonic response, implying that the atomic structure has to be taken into account to obtain quantitative predictions for realistic nanoplasmonic devices.

Quantum plasmonics: from jellium models to ab initio calculations

Abstract Light-matter interaction in plasmonic nanostructures is often treated within the realm of classical optics. However, recent experimental findings show the need to go beyond the classical models to explain and predict the plasmonic response at the nanoscale. A prototypical system is a nanoparticle dimer, extensively studied using both classical and quantum prescriptions. However, only very recently, fully ab initio time-dependent density functional theory (TDDFT) calculations of the optical response of these dimers have been carried out. Here, we review the recent work on the impact of the atomic structure on the optical properties of such systems. We show that TDDFT can be an invaluable tool to simulate the time evolution of plasmonic modes, providing fundamental understanding into the underlying microscopical mechanisms.

Many-body GW Calculations of Ground-State Properties: Quasi-2D Electron Systems and van der Waals Forces

We present GW many-body results for ground-state properties of two simple but very distinct families of inhomogeneous systems in which traditional implementations of density-functional theory (DFT) fail drastically. The GW approach gives notably better results than the well-known random-phase approximation, at a similar computational cost. These results establish GW as a superior alternative to standard DFT schemes without the expensive numerical effort required by quantum Monte Carlo simulations.

Image states in metal clusters

The existence of image states in small clusters is shown, using a quantum-mechanical many-body approach. We present image state energies and wave functions for spherical jellium clusters up to 186 atoms, calculated in the GW approximation, where G is the Greens function and W is the dynamically screened Coulomb interaction, which by construction contains the dynamic long-range correlation effects that give rise to image effects. In addition, we find that image states are also subject to quantum confinement. To extrapolate our investigations to clusters in the mesoscopic size range, we propose a semiclassical model potential, which we test against our full GW results.

Vertex corrections in localized and extended systems

Within many-body perturbation theory, we apply vertex corrections to various closed-shell atoms and to jellium, using a local approximation for the vertex consistent with starting the many-body perturbation theory from a Kohn-Sham Green’s function constructed from density-functional theory in the local-density approximation. The vertex appears in two places—in the screened Coulomb interaction W and in the self-energy —and we obtain a systematic discrimination of these two effects by turning the vertex in on and off. We also make comparisons to standard GW results within the usual random-phase approximation, which omits the vertex from both. When a vertex is included for closed-shell atoms, both ground-state and excited-state properties demonstrate little improvement over standard GW. For jellium, we observe marked improvement in the quasiparticle bandwidth when the vertex is included only in W, whereas turning on the vertex in leads to an unphysical quasiparticle dispersion and work function. A simple analysis suggests why implementation of the vertex only in W is a valid way to improve quasiparticle energy calculations, while the vertex in is unphysical, and points the way to the development of improved vertices for ab initio electronic structure calculations.

Anisotropy Effects on the Plasmonic Response of Nanoparticle Dimers

We present an ab initio study of the anisotropy and atomic relaxation effects on the optical properties of nanoparticle dimers. Special emphasis is placed on the hybridization process of localized surface plasmons, plasmon-mediated photoinduced currents, and electric-field enhancement in the dimer junction. We show that there is a critical range of separations between the clusters (0.1-0.5 nm) in which the detailed atomic structure in the junction and the relative orientation of the nanoparticles have to be considered to obtain quantitative predictions for realistic nanoplasmonic devices. It is worth noting that this regime is characterized by the emergence of electron tunneling as a response to the driven electromagnetic field. The orientation of the particles not only modifies the attainable electric field enhancement but can lead to qualitative changes in the optical absorption spectrum of the system.

Assessment of density-functional approximations: Long-range correlations and self-interaction effects

The complex nature of electron-electron correlations is made manifest in the very simple but nontrivial problem of two electrons confined within a sphere. The description of highly nonlocal correlation and self-interaction effects by widely used local and semilocal exchange-correlation energy density functionals is shown to be unsatisfactory in most cases. Even the best such functionals exhibit significant errors in the Kohn-Sham potentials and density profiles.

Diagrammatic self-energy approximations and the total particle number

There is increasing interest in many-body perturbation theory as a practical tool for the calculation of ground-state properties. As a consequence, unambiguous sum rules such as the conservation of particle number under the influence of the Coulomb interaction have acquired an importance that did not exist for calculations of excited-state properties. In this paper we obtain a rigorous, simple relation whose fulfilment guarantees particle-number conservation in a given diagrammatic self-energy approximation. Hedins G(0)W(0) approximation does not satisfy this relation and hence violates the particle-number sum rule. Very precise calculations for the homogeneous electron gas and a model inhomogeneous electron system allow the extent of the nonconservation to be estimated.

Density Functional Theories and Self-energy Approaches

One of the fundamental problems in condensed-matter physics and quantum chemistry is the theoretical study of electronic properties. This is essential to understand the behaviour of systems ranging from atoms, molecules, and nanostructures to complex materials. Since electrons are governed by the laws of quantum mechanics, the many-electron problem is, in principle, fully described by a Schrodinger equation (supposing the nuclei to be fixed). However, the electrostatic repulsion between the electrons makes its numerical resolution an impossible task in practice, even for a relatively small number of particles.