Plasmon dispersion in layered transition-metal dichalcogenides

Motivated by recent experiments, we perform a microscopic analysis of the dynamical charge response of layered transition-metal dichalcogenides that display a low-temperature charge-density wave (CDW) order. In agreement with measurements, our parameter-free results show a negative in-plane plasmon dispersion that switches to positive slope upon electron (or hole) doping. This finding is explained by the peculiar behavior of the intraband transitions, which are partially suppressed under doping, and it is not linked to the CDW order. Finally, in the direction perpendicular to the layers, we predict the reappearance around the Bragg reflections of the spectra of the first Brillouin zone, a clear effect of the crystal local-field impact. Our results give a general picture of the collective excitations in these materials suggesting a simpler reinterpretation of the experiments. © 2012 American Physical Society.Financial support was provided by Spanish (FIS2011-65702-C02-01 and PIB2010US-00652), ACI-Promociona (ACI2009-1036), and Grupos Consolidados UPV/EHU del Gobierno Vasco (IT-319-07) grants and the European Research Council Advanced Grant DYNamo (ERC-2010-AdG, Proposal No. 267374).Peer Reviewe

High-energy collective electronic excitations in layered transition-metal dichalcogenides

Under the terms of the Creative Commons Attribution License 3.0 (CC-BY).-- et al.We characterize experimentally and theoretically the collective electronic excitations in two prototypical layered transition-metal dichalcogenides, NbSe2 and Cu0.2NbS2. The energy- and momentum-dependent dynamical structure factor was measured by inelastic x-ray scattering (IXS) spectroscopy and simulated by time-dependent density-functional theory. We find good agreement between theory and experiment, provided that Nb semicore states are taken into account together with crystal local-field effects. Both materials have very similar spectra, characterized by two main plasmons at 9 and 23 eV, which we show to both have π+σ character on the basis of a detailed analysis of the band structure. Finally, we discuss the role of the layer anisotropy in the dispersion of these plasmons.We acknowledge financial support from the European Research Council Advanced Grant DYNamo (ERC-2010-AdG-267374), Spanish grant (2010-21282-C02-01), Grupos Consolidados UPV/EHU del Gobierno Vasco (IT578-13), European Commission project CRONOS (Grant No. 280879-2). This research was also supported by a Marie Curie FP7 Integration Grant within the 7th European Union Framework Programme, and by Generalidad Valenciana (ISIC Nano program). S.H., K.O.R. and C.J.S. were supported by the Academy of Finland (projects 1256211, 1254065, 1259526) and University of Helsinki Research Funds (project 490076).Peer Reviewe

Dielectric screening in two-dimensional insulators: Implications for excitonic and impurity states in graphane

For atomic thin layer insulating materials we provide an exact analytic form of the two-dimensional screened potential. In contrast to three-dimensional systems where the macroscopic screening can be described by a static dielectric constant in 2D systems the macroscopic screening is non local (q-dependent) showing a logarithmic divergence for small distances and reaching the unscreened Coulomb potential for large distances. The cross-over of these two regimes is dictated by 2D layer polarizability that can be easily computed by standard first-principles techniques. The present results have strong implications for describing gap-impurity levels and also exciton binding energies. The simple model derived here captures the main physical effects and reproduces well, for the case of graphane, the full many-body GW plus Bethe-Salpeter calculations. As an additional outcome we show that the impurity hole-doping in graphane leads to strongly localized states, what hampers applications in electronic devices. In spite of the inefficient and nonlocal two-dimensional macroscopic screening we demonstrate that a simple $\mathbf{k}\cdot\mathbf{p}$ approach is capable to describe the electronic and transport properties of confined 2D systems.Comment: 17 pages, 3 figure

Strong charge-transfer excitonic effects and Bose-Einstein exciton-condensate in graphane

Using first principles many-body theory methods (GW+BSE) we demonstrate that optical properties of graphane are dominated by localized charge-transfer excitations governed by enhanced electron correlations in a two-dimensional dielectric medium. Strong electron-hole interaction leads to the appearance of small radius bound excitons with spatially separated electron and hole, which are localized out-of-plane and in-plane, respectively. The presence of such bound excitons opens the path on excitonic Bose-Einstein condensate in graphane that can be observed experimentally.Comment: 8 pages, 6 figure

Superconducting pairing mediated by spin fluctuations from first principles

Under the terms of the Creative Commons Attribution License 3.0 (CC-BY).-- et al.We present the derivation of an ab initio and parameter-free effective electron-electron interaction that goes beyond the screened random phase approximation and accounts for superconducting pairing driven by spin fluctuations. The construction is based on many-body perturbation theory and relies on the approximation of the exchange-correlation part of the electronic self-energy within time-dependent density functional theory. This effective interaction is included in an exchange-correlation kernel for superconducting density functional theory in order to achieve a completely parameter free superconducting gap equation. First results from applying the new functional to a simplified two-band electron gas model are consistent with experiments.Peer Reviewe

Plasmon dispersion in layered transition-metal dichalcogenides

Motivated by recent experiments, we perform a microscopic analysis of the dynamical charge response of layered transition-metal dichalcogenides that display a low-temperature charge-density wave (CDW) order. In agreement with measurements, our parameter-free results show a negative in-plane plasmon dispersion that switches to positive slope upon electron (or hole) doping. This finding is explained by the peculiar behavior of the intraband transitions, which are partially suppressed under doping, and it is not linked to the CDW order. Finally, in the direction perpendicular to the layers, we predict the reappearance around the Bragg reflections of the spectra of the first Brillouin zone, a clear effect of the crystal local-field impact. Our results give a general picture of the collective excitations in these materials suggesting a simpler reinterpretation of the experiments

Excitons in van der Waals materials : From monolayer to bulk hexagonal boron nitride

We present a general picture of the exciton properties of layered materials in terms of the excitations of their single-layer building blocks. To this end, we derive a model excitonic Hamiltonian by drawing an analogy with molecular crystals, which are other prototypical van der Waals materials. We employ this simplified model to analyze in detail the excitation spectrum of hexagonal boron nitride (hBN) that we have obtained from the ab initio solution of the many-body Bethe-Salpeter equation as a function of momentum. In this way, we identify the character of the lowest-energy excitons in hBN, discuss the effects of the interlayer hopping and the electron-hole exchange interaction on the exciton dispersion, and illustrate the relation between exciton and plasmon excitations in layered materials.Peer reviewe

Electronic properties of molecular solids: the peculiar case of solid Picene

Recently, a new organic superconductor, K-intercalated Picene with high transition temperatures $T_c$ (up to 18\,K) has been discovered. We have investigated the electronic properties of the undoped relative, solid picene, using a combination of experimental and theoretical methods. Our results provide detailed insight into the occuopied and unoccupied electronic states

Instantaneous band gap collapse in photoexcited monoclinic VO2_2 due to photocarrier doping

Using femtosecond time-resolved photoelectron spectroscopy we demonstrate that photoexcitation transforms monoclinic VO$_2$ quasi-instantaneously into a metal. Thereby, we exclude an 80 femtosecond structural bottleneck for the photoinduced electronic phase transition of VO$_2$. First-principles many-body perturbation theory calculations reveal a high sensitivity of the VO$_2$ bandgap to variations of the dynamically screened Coulomb interaction, supporting a fully electronically driven isostructral insulator-to-metal transition. We thus conclude that the ultrafast band structure renormalization is caused by photoexcitation of carriers from localized V 3d valence states, strongly changing the screening \emph{before} significant hot-carrier relaxation or ionic motion has occurred

Loss spectroscopy of molecular solids: Combining experiment and theory

The nature of the lowest-energy electronic excitations in prototypical molecular solids is studied here in detail by combining electron energy loss spectroscopy (EELS) experiments and state-of-the-art many-body calculations based on the Bethe–Salpeter equation. From a detailed comparison of the spectra in picene, coronene and tetracene we generally find a good agreement between theory and experiment, with an upshift of the main features of the calculated spectrum of 0.1–0.2 eV, which can be considered the error bar of the calculation. We focus on the anisotropy of the spectra, which illustrates the complexity of this class of materials, showing a high sensitivity with respect to the three-dimensional packing of the molecular units in the crystal. The differences between the measured and the calculated spectra are explained in terms of the small differences between the crystal structures of the measured samples and the structural model used in the calculations. Finally, we discuss the role played by the different electron–hole interactions in the spectra. We thus demonstrate that the combination of highly accurate experimental EELS and theoretical analysis is a powerful tool to elucidate and understand the electronic properties of molecular solids