Monitoring the refinement of crystal structures with 15N solid-state NMR shift tensor data

Keyton Kalakewich, Robbie Iuliucci, Karl T. Mueller, Harriet Eloranta, James K. Harper

Research output: Contribution to journalArticlepeer-review

22 Scopus citations

Abstract

The 15N chemical shift tensor is shown to be extremely sensitive to lattice structure and a powerful metric for monitoring density functional theory refinements of crystal structures. These refinements include lattice effects and are applied here to five crystal structures. All structures improve based on a better agreement between experimental and calculated 15N tensors, with an average improvement of 47.0 ppm. Structural improvement is further indicated by a decrease in forces on the atoms by 2-3 orders of magnitude and a greater similarity in atom positions to neutron diffraction structures. These refinements change bond lengths by more than the diffraction errors including adjustments to X-Y and X-H bonds (X, Y = C, N, and O) of 0.028 ± 0.002 Å and 0.144 ± 0.036 Å, respectively. The acquisition of 15N tensors at natural abundance is challenging and this limitation is overcome by improved 1H decoupling in the FIREMAT method. This decoupling dramatically narrows linewidths, improves signal-to-noise by up to 317%, and significantly improves the accuracy of measured tensors. A total of 39 tensors are measured with shifts distributed over a range of more than 400 ppm. Overall, experimental 15N tensors are at least 5 times more sensitive to crystal structure than 13C tensors due to nitrogen's greater polarizability and larger range of chemical shifts.

Original languageEnglish (US)
Article number194702
JournalJournal of Chemical Physics
Volume143
Issue number19
DOIs
StatePublished - Nov 21 2015

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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