1,721,077 research outputs found
Azimuthal Dichroism in Near-Edge X-ray Absorption Fine Structure Spectra of Planar Molecules
No full textThe dependence of the near-edge X-ray absorption fine structure (NEXAFS) spectrum of molecules on the photon electric field direction is investigated by means of first-principles simulations based on density functional theory with the transition-potential approach. In addition to the well-known dependence of the NEXAFS resonances on the orientation of the electric field with respect to the molecular plane, we demonstrate that for planar molecules with sufficient in-plane anisotropy such as pentacene a dichroic effect is found with a splitting of the sigma* resonance as a function of the azimuthal orientation of the photon electric field in the molecular plane. The sigma* splitting is investigated as a function of the length of acenes and closely related molecules. A proper assignment of such spectral features guided by theory together with variable polarization experiments may allow one to completely determine the orientation of molecules at interfaces
Thermally Activated on‐Surface Self‐Metalation of Pd‐Phthalocyanines
No full textPhthalocyanines (Pcs) are essential organic molecules with wide-ranging applications in fields such as catalysis and optoelectronics, owing to their stable aromatic structure and exceptional thermal stability. Equally important is their versatility, which can be achieved by modifying the central metal atom. In this context, metalation—the process by which a central metal atom is incorporated into the macrocycle—plays a critical role in tailoring both the electronic and structural properties of Pcs. In this work, we investigate the thermally activated on-surface synthesis of palladium phthalocyanine (PdPc) by depositing metal-free phthalocyanine ((Formula presented.)) onto a Pd(001) surface in ultra-high vacuum (UHV) conditions. Using temperature-dependent X-ray photoemission spectroscopy (XPS), we analyze the evolution of the N (Formula presented.) core level signal, confirming the successful formation of PdPc. The appearance of a secondary peak in the Pd (Formula presented.) core level, attributed to Pd atoms coordinated within the phthalocyanine molecule after metalation, provides further evidence for the PdPc synthesis. Additionally, near-edge X-ray absorption fine structure (NEXAFS) reveals that no desorption or chemical degradation occurs during the process. We believe this study represents a significant step forward in the scalable synthesis of PdPc, which, like other Pd-containing organic molecules, holds great potential for applications in catalysis and cancer therapy
A competitive amino-carboxylic hydrogen bond on a gold surface
No full textAn amino-carboxylic motif is identified as a novel synthon in the formation of 2D hetero-organic architectures at surfaces. The well-defined interacting scheme we describe herein represents an ideal prototypical system for further investigation of the interaction at surfaces of the two functional groups
TiO2(110) charge donation to an extended π-conjugated molecule
No full textThe surface reduction of rutile TiO2(110) generates a state in the band gap whose excess electrons are spread among multiple sites, making the surface conductive and reactive. The charge extraction, hence the surface catalytic properties, depends critically on the spatial extent of the charge redistribution, which has been hitherto probed by small molecules that recombine at oxygen vacancy (O-vac) sites. We demonstrate by valence band resonant photoemission (RESPES) a very general charge extraction mechanism from a reduced TiO2(110) surface to an extended electron-acceptor organic molecule. Perylene-tetra-carboxylic-diimide (PTCDI) is not trapped at Ovac sites and forms a closely packed, planar layer on TiO2(110). In this configuration, the perylene core spills out the substrate excess electrons, filling the lowest unoccupied molecular orbital (LUMO). The charge transfer from the reduced surface to an extended pi-conjugated system demonstrates the universality of the injection/extraction mechanism, opening new perspectives for the coupling of reducible oxides to organic semiconductors and supported catalysts
Going Beyond Counting First Authors in Author Co-citation Analysis
Full text linkThe present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that
only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into
account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed
Variations on the Author
Full text link“Variations on the Author” discusses two of Eduardo Coutinho’s recent films (Um Dia na Vida, from 2010, and Últimas Conversas, posthumously released in 2015) and their contribution to the general question of documentary authorship. The director’s filmography is characterized by a consistent yet self-effacing form of authorial self-inscription: Coutinho often features as an interviewer that rather than express opinions propels discourses; an interviewer that is good at listening. This mode of self-inscription characterizes him as an author who is not expressive but who is nonetheless markedly present on the screen. In Um Dia na Vida, however, Coutinho is completely absent form the image, while Últimas Conversas, on the contrary, includes a confessional prologue that moves the director from the margins to the center of his films. This article examines the ways in which these works stand out in the filmography of a director who offers new insights into the notion of cinematic authorship
Appropriate Similarity Measures for Author Cocitation Analysis
Full text linkWe provide a number of new insights into the methodological discussion about author cocitation analysis. We first argue that the use of the Pearson correlation for measuring the similarity between authors’ cocitation profiles is not very satisfactory. We then discuss what kind of similarity measures may be used as an alternative to the Pearson correlation. We consider three similarity measures in particular. One is the well-known cosine. The other two similarity measures have not been used before in the bibliometric literature. Finally, we show by means of an example that our findings have a high practical relevance.information science;Pearson correlation;cosine;similarity measure;author cocitation analysis
Hydrogen capture by porphyrins at the TiO2(110) surface
Full text linkMetal-free porphyrin molecules adsorb on the rutile TiO2(110) surface with their pyrrolic nitrogen atoms atop the O-bridge rows, whereas the iminic nitrogen atoms capture two additional hydrogen atoms. Hydrogenation occurs spontaneously at room temperature, irrespective of the distance of the polypyrrolic macrocycle from the surface, as varied by changing the porphyrin functionalization
Dispelling the Myths Behind First-author Citation Counts
Full text linkWe conducted a full-scale evaluative citation analysis study of scholars in the XML research field to explore just how different from each other author rankings resulting from different citation counting methods actually are, and to demonstrate the capability of emerging data and tools on the Web in supporting more realistic citation counting methods. Our results contest some common arguments for the continued
use of first-author citation counts in the evaluation of scholars, such as high correlations between author rankings by first-author citation counts and other citation
counting methods, and high costs of using more realistic citation counting methods that are not well-supported by the ISI databases. It is argued that increasingly available digital full text research papers make it possible for citation analysis studies to go beyond what the ISI databases have directly supported and to employ more
sophisticated methods
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