Effects of Quantum Nuclear Delocalisation on NMR Parameters from Path Integral Molecular Dynamics

Abstract

Citation for published item:hr § ¡ %nsk¡ yD wrtin nd rodgkinsonD ul @PHIRA 9i'ets of quntum nuler delolistion on xw prmeters from pth integrl moleulr dynmisF9D ghemistry X iuropen journlFD PH @VAF ppF PPHIEPPHUF Further information on publisher's website:his is the peer reviewed version of the following rtileX hr § ¡ %nsk¡ yD wF nd rodgkinsonD F @PHIRAD i'ets of untum xuler helolistion on xw rmeters from th sntegrl woleulr hynmisF ghemistry E e iuropen tournlD PH @VAX PPHIEPPHUD whih hs een pulished in (nl form t httpXGGdxFdoiForgGIHFIHHPGhemFPHIQHQRWTF his rtile my e used for nonEommeril purposes in ordne with ileyEgr erms nd gonditions for selfErhivingF Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. AbstractThe influence of nuclear delocalisation on NMR chemical shifts in molecular organic solids is explored using path integral molecular dynamics (PIMD) and density functional theory calculations of shielding tensors. Nuclear quantum effects are shown to explain previously observed systematic deviations in correlations between calculated and experimental chemical shifts, with particularly large PIMD-induced changes (up to 23 ppm) observed for atoms in methyl groups. The PIMD approach also enables isotope substitution effects on chemical shifts and J couplings to be predicted in excellent agreement with experiment for both isolated molecules and molecular crystals. An approach based on convoluting calculated shielding or coupling surfaces with probability distributions of selected bond distances and valence angles obtained from PIMD simulations is used to calculate isotope effects. IntroductionThe gauge-including projector-augmented wave (GIPAW) procedure has been recently developed for the prediction of the magnetic resonance parameters in solids, [1] and the power of

Solid-state NMR and computational investigation of solvent molecule arrangement and dynamics in isostructural solvates of droperidol

“…As observed previously [37; 50] and justified theoretically [56], these plots had a non-unity slope. Linear regression was used to reference the mean experimental shift to the mean computed shielding, and to rescale the calculated shifts.…”

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

“…It has already been successfully used for calculations of deuterium isotope effects on isotropic shifts and scalar couplings in isolated halomethane. 37 Similar application to liquids is possible in principle, although significantly longer simulation times and system sizes are likely to be required in order to reach an ergodic limit. …”

“…37 This approach systematically improved the agreement between calculated and experimental 13 C chemical shifts in solids. It also provided excellent predictions of deuterium isotope effects, which are easily detectable and can convincingly manifest the quantum nature of the nuclei.…”

Exploring Systematic Discrepancies in DFT Calculations of Chlorine Nuclear Quadrupole Couplings

“…It was shown previously that a dispersion correction did not affect the calculated magnetic shielding values of solid glycine significantly when the lattice parameters were fixed during geometry optimization. 63 The centre of mass in the simulation cell was fixed to ensure into 16 beads (which was found to be satisfactory in previous studies of molecular solids at 300 K [64][65] ) and total simulation time of 10 ps were used.…”