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Evaluation of Gas-to-Liquid 17O Chemical Shift of Water : A Test Case for Molecular and Periodic Approaches

J. Chem. Theory Comput. 2018, 14, 4041−4051

Modeling liquid water features is a challenging and ongoing task that brings together a number of computational issues related to the description both of its electronic and geometrical structure. In order to go a step further in the understanding of this peculiar liquid, we present a thorough analysis of NMR gas-to-liquid 17O and 1H shifts of water using density functional theory based molecular dynamics. In order to be as consistent as possible, we consider the influence of basis sets, exchange-correlation functionals, and structural models, in both molecular and periodic schemes, to evaluate 17O and 1H nuclear shieldings. We show that strong error compensations between functional and basis-set expansion can be obtained in molecular approaches which artificially produces good 17O gas-to-liquid shifts with relatively small basis sets. We also demonstrate that, despite their ability to provide reliable liquid phase structures, generalized-gradient approximation based exchange-correlation functionals lead to strongly inconsistent values for 17O gas-to-liquid shift. This latter property is shown to be strongly influenced by intramolecular electronic delocalization, accentuated by the surrounded molecules. In contrast, 1H is less sensitive to this effect. By including a Hartree−Fock exchange term, through the use of hybrid functionals which partially correct the self-interaction error, better agreement with experimental values is obtained. The present study provides a detailed guideline to properly evaluate gas-to-liquid shifts in hydrogen bonded systems and emphasizes that, for nuclear shieldings, an accurate electronic structure evaluation prevails over the description of the liquid structure.