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Calculating NMR parameters in aluminophosphates : evaluation of dispersion correction schemes

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scottdisp_Final.pdf (8.477Mb)
Date
02/2014
Author
Sneddon, Scott
Dawson, Daniel M.
Pickard, Chris J.
Ashbrook, Sharon E.
Funder
EPSRC
EPSRC
EPSRC
EPSRC
EPSRC
Grant ID
EP/E041825/1
EP/J010510/1
EP/J501542/1
EP/J501542/1
EP/J501542/1
Keywords
Negative thermal-expansion
Quantum MAS NMR
Molecular-sieve
1st-principles calculations
Quadrupolar nuclei
Resolution
Framework
Diffraction
Phosphate
Spectroscopy
QD Chemistry
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Abstract
Periodic density functional theory (DFT) calculations have recently emerged as a popular tool for assigning solid-state nuclear magnetic resonance (NMR) spectra. However, in order for the calculations to yield accurate results, accurate structural models are also required. In many cases the structural model (often derived from crystallographic diffraction) must be optimised (i.e., to an energy minimum) using DFT prior to the calculation of NMR parameters. However, DFT does not reproduce weak long-range "dispersion'' interactions well, and optimisation using some functionals can expand the crystallographic unit cell, particularly when dispersion interactions are important in defining the structure. Recently, dispersion-corrected DFT (DFT-D) has been extended to periodic calculations, to compensate for these missing interactions. Here, we investigate whether dispersion corrections are important for aluminophosphate zeolites (AlPOs) by comparing the structures optimised by DFT and DFT-D (using the PBE functional). For as-made AlPOs (containing cationic structure-directing agents (SDAs) and framework-bound anions) dispersion interactions appear to be important, with significant changes between the DFT and DFT-D unit cells. However, for calcined AlPOs, where the SDA-anion pairs are removed, dispersion interactions appear much less important, and the DFT and DFT-D unit cells are similar. We show that, while the different optimisation strategies yield similar calculated NMR parameters (providing that the atomic positions are optimised), the DFT-D optimisations provide structures in better agreement with the experimental diffraction measurements. Therefore, it appears that DFT-D calculations can, and should, be used for the optimisation of calcined and as-made AlPOs, in order to provide the closest agreement with all experimental measurements.
Citation
Sneddon , S , Dawson , D M , Pickard , C J & Ashbrook , S E 2014 , ' Calculating NMR parameters in aluminophosphates : evaluation of dispersion correction schemes ' , Physical Chemistry Chemical Physics , vol. 16 , no. 6 , pp. 2660-2673 . https://doi.org/10.1039/c3cp54123a
Publication
Physical Chemistry Chemical Physics
Status
Peer reviewed
DOI
https://doi.org/10.1039/c3cp54123a
ISSN
1463-9076
Type
Journal article
Rights
This is the author's version of this article. The published version © 2014 The Royal Society of Chemistry is available from http://pubs.rsc.org
Collections
  • University of St Andrews Research
URI
http://hdl.handle.net/10023/5920

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