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Proton NMR relaxation from molecular dynamics: intramolecular and intermolecular contributions in water and acetonitrile

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Abstract

NMR relaxation rates for protons in liquid water and neat acetonitrile were computed based on ab initio molecular dynamics (aiMD) with forces from Kohn–Sham (KS) theory as well as force-field (FF) based classical dynamics. Intra- and intermolecular dipole–dipole contributions were separated, and nearly quantitative agreement with experiment was obtained for water. Spin-rotation (SR) contributions to the intramolecular relaxation rate in acetonitrile were computed using nuclear SR coupling tensors obtained from KS theory. Their inclusion improved the total computed intramolecular rate to within a factor of two of experiment. Insufficient sampling of rare short-time collision events between neighboring acetonitrile molecules in the simulations is hypothesized as a major source of error in the intermolecular contributions.

Graphical abstract: Proton NMR relaxation from molecular dynamics: intramolecular and intermolecular contributions in water and acetonitrile

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Publication details

The article was received on 07 Sep 2019, accepted on 21 Nov 2019 and first published on 21 Nov 2019


Article type: Paper
DOI: 10.1039/C9CP04976B
Phys. Chem. Chem. Phys., 2019, Advance Article

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    Proton NMR relaxation from molecular dynamics: intramolecular and intermolecular contributions in water and acetonitrile

    A. Philips and J. Autschbach, Phys. Chem. Chem. Phys., 2019, Advance Article , DOI: 10.1039/C9CP04976B

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