1,720,959 research outputs found
Surface effect of small nanocrystals on the accuracy of structural parameters obtained by pair distribution function analysis
No full textThe effect of the nanocrystal surface on the accuracy of average lattice parameters, crystal sizes, and mean square atom displacements (MSDs) obtained from pair distribution function (PDF) analysis of powder X-ray diffraction is investigated. A computational workflow is developed where atomistic models of gold nanocrystals with sizes between 5 and 30 nm are created by molecular dynamics simulations, diffraction data sets are computed by the Debye scattering equation over a temperature interval of 0-300 K, and PDF refinement is performed on the diffraction data by the DiffpyCMI algorithm. The accuracy of refined parameters is evaluated against real space calculations performed directly on the atomic coordinates. Results show that the performance of PDF refinement on diffraction data is temperature-dependent, and higher temperatures favor improved accuracy in refined lattice parameters, crystal sizes, and dynamic mean square atom displacements. The surface structure of nanocrystals leads to underestimated crystallographic parameters with up to 0.16, 6.6, and 15% deviation from the true lattice parameters, crystal size, and MSDs, respectively, for 5 nm gold nanocrystals at 0 K. However, with increasing crystal size and temperature, all deviations diminish such that for 30 nm gold nanocrystals at 300 K, they are calculated as 0.021, 1.67, and 11.16%.TÜBİTA
Static and dynamic atom displacements in nanocrystalline powders from diffraction analysis at finite temperature
No full textWe evaluate the accuracy of x-ray diffraction analysis performed by Rietveld refinement in extracting the static and dynamic atomic displacement parameters of spherical gold nanocrystals with sizes of 30 nm and below and within a temperature interval of 10-300 K. A self-consistent computational workflow composed of real- and reciprocal- space analyses is designed for this purpose. We obtain average lattice parameters, static and thermal atomic displacements as well as their temperature and particle size dependence in an ideally monodispersed and realistic nanocrystalline powder generated by molecular dynamics simulations. Then, we compare crystallographic parameters obtained from real- and reciprocal- space analyses to evaluate the accuracy of diffraction analysis. We also extend the comparison to local variations of crystallographic parameters in the nanocrystals and show how Rietveld refinement relates to the average parameters of the core and surface regions separately. We show that 1) average lattice parameters obtained from Rietveld refinement are greater than the mean lattice parameter of small nanocrystals and converge to the core lattice parameter with increasing particle size, 2) Rietveld refinement significantly underestimates static atom displacements of surface atoms in small nanocrystals, 3) dynamic atomic displacements in nanocrystalline gold powders are reliably obtained within 5 % error by Rietveld refinement, provided that thermal diffuse scattering is adequately removed from the diffraction data, 4) the discrepancy between real- and reciprocal-space analysis increases for the smallest gold nanocrystal.TÜBİTA
Harnessing pore size in COF membranes: A concentration gradient-driven molecular dynamics study on enhanced H2/CH4 separation
No full textThis work presents a novel approach for accurately predicting the gas transport properties of covalent organic framework (COF) membranes using a nonequilibrium molecular dynamics (NEMD) methodology called concentration gradient-driven molecular dynamics (CGD-MD). We first simulated the flux of hydrogen (H2) and methane (CH4) across two distinct COF membranes, COF-300 and COF-320, for which experimental data are available in the literature. Our CGD-MD simulation results aligned closely with the experimentally measured gas permeability and selectivity of these COF membranes. Leveraging the same methodology, we discovered promising COF candidates for H2/CH4 separation, including NPN-1, NPN-2, NPN-3, TPE-COF-I, COF-303, DMTA-TPB2, 3D-Por-COF, COF-921, COF-IM AA, TfpBDH, and PCOF-2. We then compared our findings with simulations utilizing the well-known approach that merges grand canonical Monte Carlo (GCMC) and equilibrium molecular dynamics (EMD) to predict gas adsorption and diffusion parameters in COFs. Our results showed that when the pore sizes of COF membranes are below 10 & Aring;, the choice of the method plays a significant role in determining the performance of the membranes. The GCMC+EMD approach suggested that COFs tend to exhibit CH4 selectivity when their pore limiting diameters are below 10 & Aring;, whereas the CGD-MD results reveal a preference for H2. Density functional theory calculations indicate that H2 has a lower affinity for three promising COFs, NPN-1, NPN-2, and NPN-3, compared to CH4, which results in H2 remaining unbound, while CH4 occupies all of the adsorption sites, thereby facilitating the selective recovery of H2 at the end of the separation process. We proposed a relationship between adsorption time and diffusion time, highlighting the critical role of selecting an appropriate simulation method. This relationship underscores how adsorption and diffusion processes interplay, impacting material performance. Overall, these insights not only improve the accuracy of predictive models but also guide the development of more efficient COF-based membrane applications for future research and industrial applications.TÜBİTA
Accuracy Limits of Pair Distribution Function Analysis in Structural Characterization of Nanocrystalline Powders by X-ray Diffraction
No full textWe report the minimum errors of structural parameters, namely lattice parameter, crystallite size, and atomic displacement parameters, expected from Pair Distribution Function (PDF) analysis of nanocrystalline gold powders for the first time by a self-consistent computational methodology. Although PDF analysis has been increasingly used to characterize nanocrystalline powders by X-rays, the current literature includes no established error bounds to be expected from the resulting structural parameters. For accurate interpretation of X-ray diffraction data, these error bounds must be determined, and the obtained structural parameters must be cleared from them. Our novel methodology includes: 1) simulation of ideal powder diffraction experiments with the use of the Debye scattering equation, 2) pair distribution function analysis of the diffraction data with the Diffpy-CMI analysis software, and 3) determination of the errors from PDF analysis of the simulated diffraction data by comparing them with real-space analysis of spherical gold nanocrystals that are 30 nm size and smaller. Our results show that except for the lattice parameters and even with an ideal crystalline powder sample and ideal diffraction data, the extracted structural parameters from PDF analysis diverge from their true values for the studied nanopowder. These deviations are dependent on the average size of the nanocrystals and the energy of the X-rays selected for the diffraction experiments, where lower X-ray energies and small-sized nanocrystalline powders lead to greater errors.TÜBİTAKPublisher versio
Size dependent change of mean square displacement in gold nanocrystals: A molecular dynamics simulation
No full textThermally activated atomic vibrations significantly decrease the x-ray diffraction intensities of nanocrystalline powders. Hence their quantification is critical for accurate structural characterization of small nanocrystals by x-ray diffraction. In this study, atomic vibrations in the form of mean square displacements (MSDs) in 5, 10, 15, 20, and 30 nm diameter spherical gold nanocrystals were computed by molecular dynamics (MD) simulations at room temperature and below. A strong size and temperature dependency of MSD was observed from spherical gold nanocrystals. Moreover, these displacements increased radially from the center of the nanocrystals and reached a maximum at the surface layers due to the presence of undercoordinated surface atoms and their relatively unrestricted motions. High temperature simulations were performed to investigate the evolution of structural stability of nanoparticles with increasing temperature. Surface melting was observed before complete melting of nanocrystals. Results of this work will be useful to understand the effect of nanocrystal size on the amplitude of thermally activated atomic vibrations and their quantification in measured intensities by x-ray diffraction experiments.TÜBİTA
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
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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