The effect of intermolecular interactions on the 2H and 17O quadrupole coupling constants in ice and liquid water

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Abstract
Using ab initio SCF molecular orbital techniques, the electric field gradients (efg’s) at the oxygen and hydrogen nuclei were calculated for water clusters ranging from dimer to pentamer in an attempt to reproduce the shift in 17O and 2H nuclear quadrupole coupling constants (qcc’s) that is observed on going from ice to vapor. For 2H, where the qcc shift is due mostly to the change in O–H bond length, excellent agreement with the experimental vapor → ice shift was obtained. For 17O, the change in the qcc is found to be mainly electronic in origin, effectively due to the polarization of the charge associated with the oxygen atom, and approximately 75% of the observed qcc shift was reproduced. On the basis of the calculations, estimates of the 17O and 2H qcc’s in liquid water were made that are consistent with the values obtained from an analysis of the available NMR relaxation data, provided that librational motions are properly taken into account. We also present results of SCF calculations on water interacting with a Li+, Na+, or Cl− ion, indicating that the effect of a nearby ion on the 2H and 17O qcc’s is similar to that produced by H bonding.