1. On the temperature dependence of H-U iso in the riding hydrogen model
- Author
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Francesca P. A. Fabbiani, Jens Lübben, Christian Volkmann, George M. Sheldrick, Birger Dittrich, Wolfgang Morgenroth, Alison J. Edwards, and Simon Grabowsky
- Subjects
Diffraction ,ONIOM ,Electron density ,Hydrogen ,Hirshfeld-atom refinement ,Neutron diffraction ,chemistry.chemical_element ,Synchrotron radiation ,Biochemistry ,law.invention ,Inorganic Chemistry ,riding hydrogen model ,neutron diffraction ,QM/MM computations ,invariom refinement ,synchrotron radiation ,Structural Biology ,law ,General Materials Science ,Neutron ,Physical and Theoretical Chemistry ,Physics ,Condensed Matter Physics ,Research Papers ,Synchrotron ,3. Good health ,Computational physics ,Crystallography ,chemistry - Abstract
The temperature dependence of hydrogen U iso and parent U eq in the riding hydrogen model is investigated by neutron diffraction, aspherical-atom refinements and QM/MM and MO/MO cluster calculations. Fixed values of 1.2 or 1.5 appear to be underestimated, especially at temperatures below 100 K., The temperature dependence of H-U iso in N-acetyl-l-4-hydroxyproline monohydrate is investigated. Imposing a constant temperature-independent multiplier of 1.2 or 1.5 for the riding hydrogen model is found to be inaccurate, and severely underestimates H-U iso below 100 K. Neutron diffraction data at temperatures of 9, 150, 200 and 250 K provide benchmark results for this study. X-ray diffraction data to high resolution, collected at temperatures of 9, 30, 50, 75, 100, 150, 200 and 250 K (synchrotron and home source), reproduce neutron results only when evaluated by aspherical-atom refinement models, since these take into account bonding and lone-pair electron density; both invariom and Hirshfeld-atom refinement models enable a more precise determination of the magnitude of H-atom displacements than independent-atom model refinements. Experimental efforts are complemented by computing displacement parameters following the TLS+ONIOM approach. A satisfactory agreement between all approaches is found.
- Published
- 2014