Determination of absolute configurations of crystal structures using electron diffraction patterns by means of least-squares refinement

2002 ◽  
Vol 90 (4) ◽  
pp. 291-300 ◽  
Author(s):  
J. Jansen ◽  
H.W. Zandbergen
2000 ◽  
Vol 33 (4) ◽  
pp. 1088-1101 ◽  
Author(s):  
Eva Dimmeler ◽  
Rasmus R. Schröder

Three-dimensional structure determination using electron diffraction of crystalline samples necessitates the determination of the Eulerian angles of tilted samples. For experimental tilt series, even with approximately known tilt, the resolution of the final three-dimensional reconstructions is reduced as a result of the large errors of the refined tilt angles and crystal axes positions. The presented new least-squares procedure determines the orientation of the crystal with very high accuracy from a single electron diffraction pattern. Instead of evaluating the averaged pattern geometry, each diffraction spot position is individually included in an analytical non-linear fit. This procedure is very stable against potential experimental errors, as demonstrated by Monte Carlo simulations. As a test sample, a three-dimensional microcrystal of an organic crystal compound was used. Contrary to the conventional method, which produced erroneous Miller indices for some reflections, the indexing obtained with the new algorithm was more consistent for each individual pattern. Preliminary data from frozen hydrated protein crystals, the samples of which are beam sensitive and for which only a few patterns can be recorded from a single crystal, indicate that the new angle determination promises to be particularly beneficial under such conditions.


2000 ◽  
Vol 33 (5) ◽  
pp. 1246-1252 ◽  
Author(s):  
Elizabeth J. Grier ◽  
Amanda K. Petford-Long ◽  
Roger C. C. Ward

Computer simulations of the electron diffraction patterns along the [\bar{1}10] zone axes of four ordered structures within the β-RH2+xphase, withR= Ho or Y, and 0 ≤x≤ 0.25, have been performed to establish whether or not the hydrogen ordering could be detected using electron diffraction techniques. Ordered structures within otherRH2+x(R= Ce, Tb) systems have been characterized with neutron scattering experiments; however, for HoH(D)2+x, neutron scattering failed to characterize the superstructure, possibly because of the lowxconcentration or lack of long-range order within the crystal. This paper aims to show that electron diffraction could overcome both of these problems. The structures considered were the stoichiometric face-centred cubic (f.c.c.) fluorite structure (x= 0), theD1 structure (x= 0.125), theD1astructure (x= 0.2) and theD022structure (x= 0.25). In the stoichiometric structure, with all hydrogen atoms located on the tetrahedral (t) sites, only the diffraction pattern from the f.c.c. metal lattice was seen; however, for the superstoichiometric structures, with the excess hydrogen atoms ordered on the octahedral (o) sites, extra reflections were visible. All the superstoichiometric structures showed extra reflections at the (001)f.c.c.and (110)f.c.c.type positions, with structureD1 also showing extra peaks at (½ ½ ½)f.c.c.. These reflections are not seen in the simulations at similar hydrogen concentrations with the hydrogen atoms randomly occupying theovacancies.


Author(s):  
J. Nolan ◽  
A. D. Edgar

SummaryAn X-ray investigation has been made of synthetic pyroxenes in the system acmite-diopside, crystallized at 750° C and 1000 kg/cm2 water-vapour pressure. Lattice parameters of these pyroxenes have been determined by least squares analyses of powder diffraction patterns and show an approximately linear relationship with composition, plotted as weight per cent. A rapid X-ray method has also been devised for the determination of the compositions of pyroxenes of this series.


The wave-length of electrons of energy 40 to 60 keV has been determined from the diffraction patterns of transmission specimens of alkali halides and metals. The accelerating potential was measured by a special potentiometer and hence the quantity h /√( em 0 ) was derived. The results using specimens of sodium chloride, potassium chloride, caesium iodide and aluminium were mutually consistent and their mean value was h /√( em 0 ) = (1*00156 ± 0.00010) x 10 -8 ( e in e. s. u.). Specimens of gold and lithium fluoride gave anomalous results.


1975 ◽  
Vol 30 (4) ◽  
pp. 549-553 ◽  
Author(s):  
F. Gleisberg ◽  
A. Haberl ◽  
W. Zeil

Abstract Gas electron diffraction (GED) intensities of CSFCl were measured and resulted in an ra- structure of this molecule. An rav-structure was obtained by combining our GED-data and the rotational constants reported by Kohrmann and Zeil. Both structures were found to be consistent within their uncertainties. The planar structure of CSFCl has been confirmed. A least squares analysis resulted in the following rg-distances and bond angles: r(C-Cl) =1.7178±0.0009 Å, r(C=S) =1.5931 ±0.0008 Å, r(C-F) =1.3387±0.0014 Å, ∢ S = (C-Cl)=127.28 ± 0.09°, ∢(S=C-F)= 123.58 ±0.12°.Inclusion of rotational constants into the GED-analysis allowed an experimental determination of all mean square amplitudes (MSA). We have used the valence force constants obtained by Kohrmann to evaluate the MSA theoretically. Qualitative agreement was found between the theoretical and experimental values of the MSA.


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