Interplay of Adsorption Geometry and Work Function Evolution at the TCNE/Cu(111) Interface

The adsorption of organic electron acceptors on metal surfaces is a powerful way to change the effective work function of the substrate through the formation of charge-transfer-induced dipoles. The work function of the interfaces is hence controlled by the redistribution of charges upon adsorption of the organic layer, which depends not only on the electron affinity of the organic material but also on the adsorption geometry. As shown in this work, the latter dependence controls the work function also in the case of adsorbate layers exhibiting a mixture of various adsorption geometries. Based on a combined experimental (core-level and infrared spectroscopy) and theoretical (density functional theory) study for tetracyanoethylene (TCNE) on Cu(111), we find that TCNE adsorbs in at least three different orientations, depending on TCNE coverage. At low coverage, flat lying TCNE dominates, as it possesses the highest adsorption energy. At a higher coverage, additionally, two different standing orientations are found. This is accompanied by a large increase in the work function of almost 3 eV at full monolayer coverage. Our results suggest that the large increase in work function is mainly due to the surface dipole of the free CN groups of the standing molecules and less dependent on the charge-transfer dipole of the differently oriented and charged molecules. This, in turn, opens new opportunities to control the work function of interfaces, e.g., by synthetic modification of the adsorbates, which may allow one to alter the adsorption geometries of the molecules as well as their contributions to the interface dipoles and, hence, the work function

The Magnitude of Global Marine Species Diversity

Background: The question of how many marine species exist is important because it provides a metric for how much we do and do not know about life in the oceans. We have compiled the first register of the marine species of the world and used this baseline to estimate how many more species, partitioned among all major eukaryotic groups, may be discovered. Results: There are ∼226,000 eukaryotic marine species described. More species were described in the past decade (∼20,000) than in any previous one. The number of authors describing new species has been increasing at a faster rate than the number of new species described in the past six decades. We report that there are ∼170,000 synonyms, that 58,000–72,000 species are collected but not yet described, and that 482,000–741,000 more species have yet to be sampled. Molecular methods may add tens of thousands of cryptic species. Thus, there may be 0.7–1.0 million marine species. Past rates of description of new species indicate there may be 0.5 ± 0.2 million marine species. On average 37% (median 31%) of species in over 100 recent field studies around the world might be new to science. Conclusions: Currently, between one-third and two-thirds of marine species may be undescribed, and previous estimates of there being well over one million marine species appear highly unlikely. More species than ever before are being described annually by an increasing number of authors. If the current trend continues, most species will be discovered this century

Low temperature infrared spectra of CO adsorbed on the surface of MgO(001) thin films

Reflection–absorption infrared spectra of CO adsorbed on the surface of thin MgO(0 0 1) films are reported in the temperature range 30–90 K. The observed bands are identical with those reported earlier for MgO single crystals and powder samples. By selective population of low-coordinated (LC) sites and from the analysis of respective TPD spectra a desorption energy for LC sites of ~25 kJ mol_1 was derived, in perfect agreement with recent findings on MgO powders. Experiments with 12CO/13CO give evidence for substantial infrared intensity transfer between neighboring CO oscillators and the formation of adsorbate complexes containing more than one CO molecule on low-coordinated sites