UV active plasmons in alkali and alkaline earth intercalated graphene

The interband pi and pi+sigma plasmons in pristine graphene and the Dirac plasmon in doped graphene are not applicable, since they are broad or weak, and weakly couple to an external longitudinal or electromagnetic probe. Therefore, the ab initio Density Function Theory is used to demonstrate that the chemical doping of the graphene by the alkali or alkaline earth atoms dramatically changes the poor graphene excitation spectrum in the ultra-violet frequency range (4 - 10 eV). Four prominent modes are detected. Two of them are the intra-layer plasmons with the square-root dispersion, characteristic for the two-dimensional modes. The remaining two are the inter-layer plasmons, very strong in the long-wavelength limit but damped for larger wave-vectors. The optical absorption calculations show that the inter-layer plasmons are both optically active, which makes these materials suitable for small organic molecule sensing. This is particularly intriguing because the optically active two-dimensional plasmons have not been detected in other materials

Core level spectra in XPS of pristine and doped graphene

Spectra of the C1s core hole, created in XPS and screened by electronic excitations in pristine and doped graphene, are calculated and discussed. We find that singular effects in the lineshapes are not possible in the pristine graphene, and their observation should be connected with the doping. However, the structure of the low energy excitation spectrum in the region where the singular behaviour is expected leads to asymmetries in the core hole lineshapes in pristine graphene similar to those in doped graphene. This makes the analysis more complex than in the case of metals and may lead to incorrect or incomplete interpretation of experimental results

Using surface plasmonics to turn on fullerene's dark excitons

Using our recently proposed Bethe-Salpeter $G_0W_0$ formulation, we explore the optical absorption spectra of fullerene (C$_{60}$) near coinage metal surfaces (Cu, Ag, and Au). We pay special attention to how the surface plasmon $\omega_S$ influences the optical activity of fullerene. We find the lower energy fullerene excitons at 3.77 and 4.8 eV only weakly interact with the surface plasmon. However, we find the surface plasmon strongly interacts with the most intense fullerene $\pi$ exciton, i.e.\ the dipolar mode at $\hbar\omega_+\approx$ 6.5 eV, and the quadrupolar mode at $\hbar\omega_-\approx$ 6.8 eV. When fullerene is close to a copper surface ($z_0\approx$ 5.3 \AA) the dipolar mode $\omega_+$ and "localized" surface plasmons in the molecule/surface interface hybridize to form two coupled modes which both absorb light. As a result, the molecule gains an additional optically active mode. Moreover, in resonance, when $\omega_S\approx\omega_\pm$, the strong interaction with the surface plasmon destroys the $\omega_-$ quadrupolar character and it becomes an optically active mode. In this case the molecule gains two additional very intense optically active modes. Further, we find this resonance condition, $\omega_S \approx \omega_\pm$, is satisfied by silver and gold metal surfaces.Comment: 10 pages, 8 figure

Optical absorption and conductivity in quasi-two-dimensional crystals from first principles: Application to graphene

This paper gives a theoretical formulation of the electromagnetic response of the quasi-two-dimensional (Q2D) crystals suitable for investigation of optical activity and polariton modes. The response to external electromagnetic field is described by current-current response tensor $\Pi_{\mu\nu}$ calculated by solving the Dyson equation in the random phase approximation (RPA), where current-current interaction is mediated by the photon propagator $D_{\mu\nu}$. The irreducible current-current response tensor $\Pi^0_{\mu\nu}$ is calculated from the {\em ab initio} Kohn-Sham (KS) orbitals. The accuracy of $\Pi^0_{\mu\nu}$ is tested in the long wavelength limit where it gives correct Drude dielectric function and conductivity. The theory is applied to the calculation of optical absorption and conductivity in pristine and doped single layer graphene and successfully compared with previous calculations and measurements

Changing character of electronic transitions in graphene: From single particle excitations to plasmons

In this paper we clarify the nature of $\pi$ and $\pi+\sigma$ electron excitations in pristine graphene. We clearly demonstrate the continuous transition from single particle to collective character of such excitations and how screening modifies their dispersion relations. We prove that $\pi$ and $\pi+\sigma$ plasmons do exist in graphene, though occurring only for a particular range of wavevectors and with finite damping rate. The particular attention is paid to compare the theoretical results with available EELS measurements in optical ($\mathrm{Q\approx 0}$) and other ($\mathrm{Q\neq 0}$) limits. The conclusions, based on microscopic numerical results, are confirmed in an approximate analytical approach

Mechanism of metallization and superconductivity suppression in YBa2(_2(Cu0.97_{0.97}Zn0.03)3_{0.03})_3O6.92_{6.92} revealed by 67^{67}Zn NQR

We measure the nuclear quadrupole resonance (NQR) signal on the Zn site in nearly optimally doped YBa$_2$Cu$_3$O$_{6.92}$, when Cu is substituted by 3\% of isotopically pure $^{67}$Zn. We observe that Zn creates large insulating islands, confirming two earlier conjectures: that doping provokes an orbital transition in the CuO$_2$ plane, which is locally reversed by Zn substitution, and that the islands are antiferromagnetic. Also, we find that the Zn impurity locally induces a breaking of the D$_4$ symmetry. Cluster and DFT calculations show that the D$_4$ symmetry breaking is due to the same partial lifting of degeneracy of the nearest-neighbor oxygen sites as in the LTT transition in La$_{2-x}$Ba$_x$CuO$_4$, similarly well-known to strongly suppress superconductivity. These results show that in-plane oxygen $2p^5$ orbital configurations are principally involved in the metallicity and superconductivity of all high-T$_c$ cuprates, and provide a qualitative symmetry-based constraint on the SC mechanism.Comment: extended version, to appear in New Journal of Physic

Quasiparticle spectra and excitons of organic molecules deposited on substrates: G0W0-BSE approach applied to benzene on graphene and metallic substrates

We present an alternative methodology for calculating the quasi-particle energy, energy loss, and optical spectra of a molecule deposited on graphene or a metallic substrate. To test the accuracy of the method it is first applied to the isolated benzene (C6H6) molecule. The quasiparticle energy levels and especially the energies of the benzene excitons (triplet, singlet, optically active and inactive) are in very good agreement with available experimental results. It is shown that the vicinity of the various substrates (pristine/doped graphene or (jellium) metal surface) reduces the quasiparticle HOMO-LUMO gap by an amount that slightly depends on the substrate type. This is consistent with the simple image theory predictions. It is even shown that the substrate does not change the energy of the excitons in the isolated molecule. We prove (in terms of simple image theory) that energies of the excitons are indeed influenced by two mechanisms which cancel each other. We demonstrate that the benzene singlet optically active (E1u) exciton couples to real electronic excitations in the substrate. This causes it substantial decay, such as {\Gamma} = 174 meV for pristine graphene and {\Gamma} = 362 meV for metal surfaces as the substrate. However, we find that doping graphene does not influence the E1u exciton decay rate.Comment: 16 pages, 14 figure

Benchmarking van der Waals functionals with noncontact RPA calculations on graphene-Ag(111)

Under the terms of the Creative Commons Attribution License 3.0 (CC-BY).We have benchmarked long range behavior of seven different van der Waals functionals comparing them with our ACF-RPA correlation calculations for graphene on a Ag(111) system. Correlation given by the second version of van der Waals density functional vdW-DF2 agrees remarkably well with our random phase approximation (RPA) calculation in the long range region. In the intermediate and shorter range regions combining vdW-DF2 correlation with proper exchange functional becomes important. We compared the results of the van der Waals functionals in this region to the previous RPA calculations and to some extent to experimental observations, and calculated that the combined vdW-DF2(C09x) or rev-vdW-DF2 functionals show satisfactory behavior.Peer Reviewe

Benchmarking van der Waals functionals with noncontact RPA calculations on graphene-Ag(111)

We have benchmarked long range behavior of seven different van der Waals functionals comparing them with our ACF-RPA correlation calculations for graphene on a Ag(111) system. Correlation given by the second version of van der Waals density functional vdW-DF2 agrees remarkably well with our random phase approximation (RPA) calculation in the long range region. In the intermediate and shorter range regions combining vdW-DF2 correlation with proper exchange functional becomes important. We compared the results of the van der Waals functionals in this region to the previous RPA calculations and to some extent to experimental observations, and calculated that the combined vdW-DF2(C09x) or rev-vdW-DF2 functionals show satisfactory behavior