Temperature Dependence of NMR Parameters Calculated from Path Integral Molecular Dynamics Simulations

0459058 - ÚOCHB 2017 RIV US eng J - Journal Article
Dračínský, Martin - Bouř, Petr - Hodgkinson, P.
Temperature Dependence of NMR Parameters Calculated from Path Integral Molecular Dynamics Simulations.
Journal of Chemical Theory and Computation. Roč. 12, č. 3 (2016), s. 968-973. ISSN 1549-9618. E-ISSN 1549-9626
R&D Projects: GA ČR GA15-11223S; GA ČR GA15-09072S; GA ČR(CZ) GA16-05935S
Institutional support: RVO:61388963
Keywords : short hydrogen bonds * density functional theory * spin coupling constants
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 5.245, year: 2016

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.
Permanent Link: http://hdl.handle.net/11104/0259315