HAB79: A New Molecular Dataset for Benchmarking DFT and DFTB Electronic Couplings Against High-Level Ab-initio Calculations

A new molecular dataset called HAB79 is introduced to provide ab-initio reference values for electronic couplings (transfer integrals) and to benchmark density functional theory (DFT) and density functional tight-binding (DFTB) calculations. The HAB79 dataset is comprised of 79 planar heterocyclic polyaromatic hydrocarbon molecules frequently encountered in organic (opto)electronics, arranged to 921 structurally diverse dimer configurations. We show that CASSCF/NEVPT2 with a minimal active space provides a robust reference method that can be applied to the relatively large molecules of the dataset. Electronic couplings are largest for cofacial dimers, in particular sulfur-containing polyaromatic hydrocarbons, with values in excess of 0.5 eV, followed by parallel displaced cofacial dimers. V-shaped dimer motifs, often encountered in the herringbone layers of organic crystals, exhibit medium-sized couplings whereas T-shaped dimers have the lowest couplings. DFT values obtained from the projector operator-based diabatization (POD) method are initially benchmarked against the smaller databases HAB11 (HAB7-) and found to systematically improve when climbing Jacob's ladder, giving mean relative unsigned errors (MRUE) of 27.7% (26.3%) for the GGA functional BLYP, 20.7% (15.8%) for hybrid functional B3LYP and 5.2% (7.5%) for the long-range corrected hybrid functional omega-B97X. Cost effective POD in combination with a GGA functional (PBE) and very efficient DFTB calculations on the dimers of the HAB79 database give a good linear correlation with the CASSCF/NEVPT2 reference data, which, after scaling with a multiplicative constant, gives reasonably small MRUEs of 17.9% and 40.1%, respectively, bearing in mind that couplings in HAB79 vary over 4 orders of magnitude

Composition of Ices in Low-Mass Extrasolar Planets

We study the formation conditions of icy planetesimals in protoplanetary disks in order to determine the composition of ices in small and cold extrasolar planets. Assuming that ices are formed from hydrates, clathrates, and pure condensates, we calculate their mass fractions with respect to the total quantity of ices included in planetesimals, for a grid of disk models. We find that the composition of ices weakly depends on the adopted disk thermodynamic conditions, and is rather influenced by the initial composition of the gas phase. The use of a plausible range of molecular abundance ratios and the variation of the relative elemental carbon over oxygen ratio in the gas phase of protoplanetary disks, allow us to apply our model to a wide range of planetary systems. Our results can thus be used to constrain the icy/volatile phase composition of cold planets evidenced by microlensing surveys, hypothetical ocean-planets and carbon planets, which could be detected by Corot or Kepler.Comment: Accepted for publication in The Astrophysical Journa

A frozen super-Earth orbiting a star at the bottom of the Main Sequence

We observed the microlensing event MOA-2007-BLG-192 at high angular resolution in JHKs with the NACO adaptive optics system on the VLT while the object was still amplified by a factor 1.23 and then at baseline 18 months later. We analyzed and calibrated the NACO photometry in the standard 2MASS system in order to accurately constrain the source and the lens star fluxes. We detect light from the host star of MOA-2007-BLG-192Lb, which significantly reduces the uncertainties in its char- acteristics as compared to earlier analyses. We find that MOA-2007-BLG-192L is most likely a very low mass late type M-dwarf (0.084 [+0.015] [-0.012] M\odot) at a distance of 660 [+100] [-70] pc orbited by a 3.2 [+5.2] [-1.8] M\oplus super-Earth at 0.66 [+0.51] [-0.22] AU. We then discuss the properties of this cold planetary system.Comment: published version A&A 540, A78 (2012) A&A, 10 pages, 7 Figure

EUCLID : Dark Universe Probe and Microlensing planet Hunter

There is a remarkable synergy between requirements for Dark Energy probes by cosmic shear measurements and planet hunting by microlensing. Employing weak and strong gravitational lensing to trace and detect the distribution of matter on cosmic and Galactic scales, but as well as to the very small scales of exoplanets is a unique meeting point from cosmology to exoplanets. It will use gravity as the tool to explore the full range of masses not accessible by any other means. EUCLID is a 1.2m telescope with optical and IR wide field imagers and slitless spectroscopy, proposed to ESA Cosmic Vision to probe for Dark Energy, Baryonic acoustic oscillation, galaxy evolution, and an exoplanet hunt via microlensing. A 3 months microlensing program will already efficiently probe for planets down to the mass of Mars at the snow line, for free floating terrestrial or gaseous planets and habitable super Earth. A 12+ months survey would give a census on habitable Earth planets around solar like stars. This is the perfect complement to the statistics that will be provided by the KEPLER satellite, and these missions combined will provide a full census of extrasolar planets from hot, warm, habitable, frozen to free floating.Comment: 6 pages 3 figures, invited talk in Pathways towards habitable planets, Barcelona, Sept 200

Aerobic Damage to [FeFe]-Hydrogenases: Activation Barriers for the Chemical Attachment of O2.

[FeFe]-hydrogenases are the best natural hydrogen-producing enzymes but their biotechnological exploitation is hampered by their extreme oxygen sensitivity. The free energy profile for the chemical attachment of O2 to the enzyme active site was investigated by using a range-separated density functional re-parametrized to reproduce high-level ab initio data. An activation free-energy barrier of 13 kcal mol(-1) was obtained for chemical bond formation between the di-iron active site and O2 , a value in good agreement with experimental inactivation rates. The oxygen binding can be viewed as an inner-sphere electron-transfer process that is strongly influenced by Coulombic interactions with the proximal cubane cluster and the protein environment. The implications of these results for future mutation studies with the aim of increasing the oxygen tolerance of this enzyme are discussed

Limb-darkening measurements for a cool red giant in microlensing event OGLE 2004-BLG-482

Aims: We present a detailed analysis of OGLE 2004-BLG-482, a relatively high-magnification single-lens microlensing event which exhibits clear extended-source effects. These events are relatively rare, but they potentially contain unique information on the stellar atmosphere properties of their source star, as shown in this study. Methods: Our dense photometric coverage of the overall light curve and a proper microlensing modelling allow us to derive measurements of the OGLE 2004-BLG-482 source star's linear limb-darkening coefficients in three bands, including standard Johnson-Cousins I and R, as well as in a broad clear filter. In particular, we discuss in detail the problems of multi-band and multi-site modelling on the expected precision of our results. We also obtained high-resolution UVES spectra as part of a ToO programme at ESO VLT from which we derive the source star's precise fundamental parameters. Results: From the high-resolution UVES spectra, we find that OGLE 2004-BLG-482's source star is a red giant of MK type a bit later than M3, with Teff = 3667 +/- 150 K, log g = 2.1 +/- 1.0 and an assumed solar metallicity. This is confirmed by an OGLE calibrated colour-magnitude diagram. We then obtain from a detailed microlensing modelling of the light curve linear limb-darkening coefficients that we compare to model-atmosphere predictions available in the literature, and find a very good agreement for the I and R bands. In addition, we perform a similar analysis using an alternative description of limb darkening based on a principal component analysis of ATLAS limb-darkening profiles, and also find a very good agreement between measurements and model predictions.Comment: Accepted in A&

Theoretical investigation of hydrogen storage in metal-intercalated graphitic materials

We have used first-principles methods to investigate how metal atoms dispersed in the interlayer space of graphitic materials affect their hydrogen-binding properties. We have considered ideal stage-one metal-intercalated graphites of various compositions as representative model systems. Our calculations suggest that alkaline earth metals can significantly enhance the hydrogen storage properties: for example, Be and Mg atoms would act as binding sites of three or four hydrogen molecules, with binding energies per H$_2$ in the 0.2--0.7 eV range, as required for applications. We also find that alkali and transition metals are not as effective in enhancing the storage capacity.Comment: 11 pages with 4 figures embedded. More information at http://www.icmab.es/dmmis/leem/jorge