The influence of temperature on NMR chemical shifts and quadrupolar couplings in model molecular organic solids is explored using path integral molecular dynamics (PIMD) and density functional theory (DFT) calculations of shielding and electric field gradient (EFG) tensors. An approach based on convoluting calculated shielding or EFG tensor components with probability distributions of selected bond distances and valence angles obtained from DFT-PIMD simulations at several temperatures is used to calculate the temperature effects. The probability distributions obtained from the quantum PIMD simulations, which includes nuclear quantum effects, are significantly broader and less temperature dependent than those obtained with conventional DFT molecular dynamics or with 1D scans through the potential energy surface. Predicted NMR observables for the model systems were in excellent agreement with experimental data.

Department of Chemistry Durham University South Road DH1 3LE Durham United Kingdom

Institute of Organic Chemistry and Biochemistry Flemingovo nám 2 16610 Prague Czech Republic

References provided by Crossref.org

The need for operando modelling of 27Al NMR in zeolites: the effect of temperature, topology and water

Analyzing Discrepancies in Chemical-Shift Predictions of Solid Pyridinium Fumarates

Dimerization of Acetic Acid in the Gas Phase-NMR Experiments and Quantum-Chemical Calculations

Exploring Accuracy Limits of Predictions of the 1H NMR Chemical Shielding Anisotropy in the Solid State

Dihydrogen contacts observed by through-space indirect NMR coupling