Validation of experimental molecular crystal structures with dispersion-corrected density functional theory calculations
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The accuracy of a dispersion-corrected density functional theory method is validated against 241 experimental organic crystal structures from Acta Cryst.Abstract:
This paper describes the validation of a dispersion-corrected density functional theory (d-DFT) method for the purpose of assessing the correctness of experimental organic crystal structures and enhancing the information content of purely experimental data. 241 experimental organic crystal structures from the August 2008 issue of Acta Cryst. Section E were energy-minimized in full, including unit-cell parameters. The differences between the experimental and the minimized crystal structures were subjected to statistical analysis. The r.m.s. Cartesian displacement excluding H atoms upon energy minimization with flexible unit-cell parameters is selected as a pertinent indicator of the correctness of a crystal structure. All 241 experimental crystal structures are reproduced very well: the average r.m.s. Cartesian displacement for the 241 crystal structures, including 16 disordered structures, is only 0.095 A (0.084 A for the 225 ordered structures). R.m.s. Cartesian displacements above 0.25 A either indicate incorrect experimental crystal structures or reveal interesting structural features such as exceptionally large temperature effects, incorrectly modelled disorder or symmetry breaking H atoms. After validation, the method is applied to nine examples that are known to be ambiguous or subtly incorrect.read more
Citations
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Anna V. Vologzhanina,Anton V. Savchenkov,Artem O. Dmitrienko,Alexander A. Korlyukov,Alexander A. Korlyukov,Ivan S. Bushmarinov,Denis V. Pushkin,Larisa B. Serezhkina +7 more
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Towards the systematic crystallisation of molecular ionic cocrystals: insights from computed crystal form landscapes
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Anisotropic thermal motion in transition-metal carbonyls from experiments and ab initio theory.
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Lattice thermal expansion and anisotropic displacements in urea, bromomalonic aldehyde, pentachloropyridine, and naphthalene
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Resolving alternative organic crystal structures using density functional theory and NMR chemical shifts.
TL;DR: Alternative (‘repeat’) determinations of organic crystal structures deposited in the Cambridge Structural Database are analysed to characterise the nature and magnitude of the differences between structure solutions obtained by diffraction methods.
References
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