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

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