How does the NMR thermometer work? Application of combined quantum molecular dynamics and GIPAW calculations into the...

Lead nitrate is an inorganic salt, commonly used for the accurate temperature determination in the solid state NMR spectroscopy, due to the strong temperature dependence of the ²⁰⁷ Pb chemical shift. As the reason for this phenomenon remained unknown, the main purpose of this study was to explain this temperature dependence at the molecular level. To achieve this, combined CASTEP geometry optimization, quantum molecular dynamics at chosen temperatures and GIPAW NMR computations were performed. Due to the previous literature reports on inaccuracy in the calculation of ²⁰⁷ Pb NMR parameters using GIPAW, a large emphasis was put on the optimization of computational method. The application of quantum molecular dynamics provided the simulation of the temperature-dependent vibrational motions and enabled to accurately compute the changes in the value of Pb δ_iso resulting from them. © 2018 Wiley Periodicals, Inc.