A library of ab initio Raman spectra for automated identification of 2D materials

Raman spectroscopy is frequently used to identify composition, structure and layer thickness of 2D materials. Here, we describe an efficient first-principles workflow for calculating resonant first-order Raman spectra of solids within third-order perturbation theory employing a localized atomic orbital basis set. The method is used to obtain the Raman spectra of 733 different monolayers selected from the computational 2D materials database (C2DB). We benchmark the computational scheme against available experimental data for 15 known monolayers. Furthermore, we propose an automatic procedure for identifying a material based on an input experimental Raman spectrum and illustrate it for the cases of MoS$_2$ (H-phase) and WTe$_2$ (T$^\prime$-phase). The Raman spectra of all materials at different excitation frequencies and polarization configurations are freely available from the C2DB. Our comprehensive and easily accessible library of \textit{ab initio} Raman spectra should be valuable for both theoreticians and experimentalists in the field of 2D materialsComment: 17 pages, 7 figure

Renormalization of Optical Excitations in Molecules near a Metal Surface

The lowest electronic excitations of benzene and a set of donor-acceptor molecular complexes are calculated for the gas phase and on the Al(111) surface using the many-body Bethe-Salpeter equation (BSE). The energy of the charge-transfer excitations obtained for the gas phase complexes are found to be around 10% lower than the experimental values. When the molecules are placed outside the surface, the enhanced screening from the metal reduces the exciton binding energies by several eVs and the transition energies by up to 1 eV depending on the size of the transition-generated dipole. As a striking consequence we find that close to the metal surface the optical gap of benzene can exceed its quasiparticle gap. A classical image charge model for the screened Coulomb interaction can account for all these effects which, on the other hand, are completely missed by standard time-dependent density functional theory.Comment: 4 pages, 3 figures; revised versio

The age of 47Tuc from self-consistent isochrone fits to colour-magnitude diagrams and the eclipsing member V69

Our aim is to derive a self-consistent age, distance and composition for the globular cluster $47\,$Tucanae ($47\,$Tuc; NGC104). First, we reevaluate the reddening towards the cluster resulting in a nominal $E(B-V)=0.03\pm0.01$ as the best estimate. The $T_{\rm eff}$ of the components of the eclipsing binary member V69 is found to be $5900\pm72$ K from both photometric and spectroscopic evidence. This yields a true distance modulus $(m-M)_0=13.21\pm0.06$(random)$\pm0.03$(systematic) to $47\,$Tuc when combined with existing measurements of V69 radii and luminosity ratio. We then present a new completely self-consistent isochrone fitting method to ground based and $\textit{HST}$ cluster colour-magnitude diagrams and the eclipsing binary member V69. The analysis suggests that the composition of V69, and by extension one of the populations of $47\,$Tuc, is given by [Fe/H]$\sim-0.70$, [O/Fe]$\sim+0.60$, and $Y\sim0.250$ on the solar abundance scale of Asplund, Grevesse & Sauval. However, this depends on the accuracy of the model $T_{\rm eff}$ scale which is 50-75 K cooler than our best estimate but within measurement uncertainties. Our best estimate of the age of $47\,$Tuc is 11.8 Gyr, with firm ($3 \sigma$) lower and upper limits of 10.4 and 13.4 Gyr, respectively, in satisfactory agreement with the age derived from the white dwarf cooling sequence if our determination of the distance modulus is adopted.Comment: 19 pages, 8 figures, accepted for publication in MNRA

Benchmarking GW against exact diagonalization for semi-empirical models

We calculate groundstate total energies and single-particle excitation energies of seven pi conjugated molecules described with the semi-empirical Pariser-Parr-Pople (PPP) model using self-consistent many-body perturbation theory at the GW level and exact diagonalization. For the total energies GW captures around 65% of the groundstate correlation energy. The lowest lying excitations are overscreened by GW leading to an underestimation of electron affinities and ionization potentials by approximately 0.15 eV corresponding to 2.5%. One-shot G_0W_0 calculations starting from Hartree-Fock reduce the screening and improve the low-lying excitation energies. The effect of the GW self-energy on the molecular excitation energies is shown to be similar to the inclusion of final state relaxations in Hartree-Fock theory. We discuss the break down of the GW approximation in systems with short range interactions (Hubbard models) where correlation effects dominate over screening/relaxation effects. Finally we illustrate the important role of the derivative discontinuity of the true exchange-correlation functional by computing the exact Kohn-Sham levels of benzene.Comment: 9 pages, 5 figures, accepted for publication in Phys. Rev.

Electron transport through an interacting region: The case of a nonorthogonal basis set

The formula derived by Meir and Wingreen [Phys. Rev. Lett. {\bf 68}, 2512 (1992)] for the electron current through a confined, central region containing interactions is generalized to the case of a nonorthogonal basis set. As in the original work, the present derivation is based on the nonequilibrium Keldysh formalism. By replacing the basis functions of the central region by the corresponding elements of the dual basis, the lead- and central region-subspaces become mutually orthogonal. The current formula is then derived in the new basis, using a generalized version of second quantization and Green's function theory to handle the nonorthogonality within each of the regions. Finally, the appropriate nonorthogonal form of the perturbation series for the Green's function is established for the case of electron-electron and electron-phonon interactions in the central region.Comment: Added references. 8 pages, 1 figur

Spin coherence times of point defects in two-dimensional materials from first principles

The spin coherence times of 69 triplet defect centers in 45 different 2D host materials are calculated using the cluster correlation expansion (CCE) method with parameters of the spin Hamiltonian obtained from density functional theory (DFT). Several of the triplets are found to exhibit extraordinarily large spin coherence times making them interesting for quantum information processing. The dependence of the spin coherence time on various factors, including the hyperfine coupling strength, the dipole-dipole coupling, and the nuclear g-factors, are systematically investigated. The analysis shows that the spin coherence time is insensitive to the atomistic details of the defect center and rather is dictated by the nuclear spin properties of the host material. Symbolic regression is then used to derive a simple expression for spin coherence time, which is validated on a test set of 55 doublet defects unseen by the regression model. The simple expression permits order-of-magnitude estimates of the spin coherence time without expensive first principles calculations

Defect Tolerant Monolayer Transition Metal Dichalcogenides

Localized electronic states formed inside the band gap of a semiconductor due to crystal defects can be detrimental to the material's optoelectronic properties. Semiconductors with lower tendency to form defect induced deep gap states are termed defect tolerant. Here we provide a systematic first principles investigation of defect tolerance in 29 monolayer transition metal dichalcogenides (TMDs) of interest for nanoscale optoelectronics. We find that the TMDs based on group VI and X metals form deep gap states upon creation of a chalcogen (S, Se, Te) vacancy while the TMDs based on group IV metals form only shallow defect levels and are thus predicted to be defect tolerant. Interestingly, all the defect sensitive TMDs have valence and conduction bands with very similar orbital composition. This indicates a bonding/anti-bonding nature of the gap which in turn suggests that dangling bonds will fall inside the gap. These ideas are made quantitative by introducing a descriptor that measures the degree of similarity of the conduction and valence band manifolds. Finally, the study is generalized to non-polar nanoribbons of the TMDs where we find that only the defect sensitive materials form edge states within the band gap

'Rapid fire' spectroscopy of Kepler solar-like oscillators

The NASA Kepler mission has been continuously monitoring the same field of the sky since the successful launch in March 2009, providing high-quality stellar lightcurves that are excellent data for asteroseismology, far superior to any other observations available at the present. In order to make a meaningful analysis and interpretation of the asteroseismic data, accurate fundamental parameters for the observed stars are needed. The currently available parameters are quite uncertain as illustrated by e.g. Thygesen et al. (A&A 543, A160, 2012), who found deviations as extreme as 2.0 dex in [Fe/H] and log g, compared to catalogue values. Thus, additional follow-up observations for these targets are needed in order to put firm limits on the parameter space investigated by the asteroseismic modellers. Here, we propose a metod for deriving accurate metallicities of main sequence and subgiant solar-like oscillators from medium resolution spectra with a moderate S/N. The method takes advantage of the additional constraints on the fundamental parameters, available from asteroseismology and multi-color photometry. The approach enables us to reduce the analysis overhead significantly when doing spectral synthesis, which in turn will increases the efficiency of follow-up observations.Comment: 3 pages, 2 figures. Proceedings from Asteroseismology of Stellar Populations in the Milky Way 2013 to appear in 'Astrophysics and Space Science Proceedings