Crystal structure and electronic states of tripotassium picene

The crystal structure of potassium doped picene with an exact stoichiometry (K3C22H14, K3picene from here onwards) has been theoretically determined within Density Functional Theory allowing complete variational freedom of the crystal structure parameters and the molecular atomic positions. A modified herringbone lattice is obtained in which potassium atoms are intercalated between two paired picene molecules displaying the two possible orientations in the crystal.Along the c-axis, organic molecules alternate with chains formed by three potassium atoms. The electronic structureof the doped material resembles pristine picene, except that now the bottom of the conduction band is occupied by six electrons coming from the ionized K atoms (six per unit cell). Wavefunctions remain based mainly on picene molecular orbitals getting their dispersion from intralayer edge to face CH/pi bonding, while eigenenergies have been modified by the change in the electrostatic potential. The small dispersion along the c-axis is assigned to small H-H overlap. From the calculated electronic density of states we expect metallic behavior for potassium doped picene.Comment: Published version: 8 twocolumn pages, 7 color figures, 2 structural .cif files include

The role of potassium orbitals in the metallic behavior of K3picene

Detailed electronic structure calculations of picene clusters doped by potassium modeling the crystalline K3picene structure show that while two electrons are completely transferred from potassium atoms to the LUMO of pristine picene, the third one remains closely attached to both material components. Multiconfigurational analysis is necessary to show that many structures of almost degenerate total energies compete to define the cluster ground state. Our results prove that the 4s orbital of potassium should be included in any interaction model describing the material. We propose a quarter filled two orbital model as the most simple model capable of describing the electronic structure of K-intercalated picene. Precise solutions obtained by a development of Lanczos method show low energy electronic excitations involving orbitals located at different positions. Consequently, metallic transport is possible in spite of the clear dominance of interaction over hopping.Comment: 12 pages, 10 figures (6 of them really heavy

Time variability of cyclonic geostrophic circulation in the Mediterranean

Interannual variability and trends of the surface geostrophic cyclonic circulation and cyclone frequency in Western and Eastern Mediterranean areas are analyzed, based on a cyclone data base derived from the ERA-40 ECWMF reanalysis (within the MEDEX project tasks), spanning from September/1957 to August/2002. In this 45 years, the cyclonic circulation show a significant decrease in the Western Mediterranean, mostly in winter and spring, and an increase in the Eastern, mainly due to the summer and autumn increase in the frequency of thermal lows

Acquisition of Demonstratives in English and Spanish

The present work re-evaluates the long-standing claim that demonstratives are among infants’ earliest and most common words. Although demonstratives are deictic words important for joint attention, deictic gestures and non-word vocalizations could serve this function in early language development; the role of demonstratives may have been overestimated. Using extensive data from the CHILDES corpora (Study 1, N = 66, 265 transcripts) and McArthur-Bates CDI database (Study 2, N = 950), the language production of 18- to 24-month-old Spanish- and English-speaking children was analyzed to determine the age and order of acquisition, and frequency of demonstratives. Results indicate that demonstratives do not typically appear before the 50th word and only become frequent from the two-word utterance stage. Corpus data show few differences between Spanish and English, whereas parental report data suggest much later acquisition for demonstratives in English. These findings expand our knowledge of the foundations of deictic communication, and of the methodological challenges of assessing early production of function words

Libanon : Heiße Spuren im „Mordfall Hariri“?

The teleosts Chelidonichthys cuculus, Trigloporus lastoviza, Serranus cabrilla and Trachinus draco, are important by-catch species, in terms of landed biomass and commercial value, from the continental shelf bottom trawl fishery off the Balearic Islands (western Mediterranean). The main biological parameters of these species were calculated from monthly biological samplings, and were used along with three years pseudo-cohorts (2008-2010) obtained from monitoring on-board of the bottom trawl fleet, to assess their exploitation level through Virtual Population Analysis (VPA) and Yield per Recruit (Y/R) analysis. Time series of fishery independent indicators based on MEDITS surveys data such as the evolution of the abundance and biomass, the distribution range, and the Conservation Status of Fish b (CSFb), were also analyzed. All four species analyzed showed growth overfishing. The reductions of the fishing effort required to reach the Y/RF0,1 reference point were lower, 66-73% depending on the species, to those reported for the target species M. merluccius (87%), but higher than that reported for M. surmuletus (53%), in the study area in the period 2000-2010. The abundance and biomass, and the distribution range did not show any trend for the period 2001-2011, whereas the CSFb showed signs of recovery that may be due to the displacement of the trawl fishing effort from the shelf to the slope during the last decade. Our results underline the necessary incorporation of monitoring and assessment of by-catch species to the management of fisheries as their populations can show a more pronounced overexploitation than target ones

Extrusión del componente plástico de la copa acetabular sin luxación protésica: a propósito de un caso

Se present a un caso de extrusión del component e plástic o (polietileno) ocurrido en el transcurso del primer me s del postoperatorio en un pacient e que había sufrido un recambio del component e acetabular. Se destaca el hecho de que cursase de forma asintomática y de que no se acompañase de luxación de la prótesis.A case of disassembly of the polyethylene component of the acetabular cup acurred in a patient one mouth after revision surgery for loosening of a screwed acetabular cup is reported. Special emphasis is made in the asyntomati c clinic and on the no association with dislocation of the femoral component