Calculation of NMR chemical shifts in organic solids: accounting for motional effects.
NMR chemical shifts were calculated from first principles for well defined crystalline organic solids. These density functional theory calculations were carried out within the plane-wave pseudopotential framework, in which truly extended systems are implicitly considered. The influence of motional effects was assessed by averaging over vibrational modes or over snapshots taken from ab initio molecular dynamics simulations. It is observed that the zero-point correction to chemical shifts can be significant, and that thermal effects are particularly noticeable for shielding anisotropies and for a temperature-dependent chemical shift. This study provides insight into the development of highly accurate first principles calculations of chemical shifts in solids, highlighting the role of motional effects on well defined systems.
Dumez
Jean-Nicolas
JN
School of Physics and Astronomy, University of St-Andrews, St Andrews KY16 9SS, United Kingdom. jeannicolas.dumez@ens-lyon.fr
Pickard
Chris J
CJ
D003460:Crystallization; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D008958:Models, Molecular; D009038:Motion; D009930:Organic Chemicals / Q000737:chemistry*
D009930:Organic Chemicals