Deuterium quadrupole coupling tensors in methyl halides: Ab initio effective core potential and liquid crystal nuclear magnetic resonance study J. Chem. Phys. 107, 1744 (1997) The quadrupole coupling constant and asymmetry parameter for the deuteron in liquid heavy water was determined using purely theoretical methods. Molecular-dynamics simulations with the ab initio potential-energy surface of Lie and Clementi were used to generate snapshots of the liquid. The electric-field gradient at the deuteron was then calculated for these configurations and averaged to obtain the liquid quadrupole coupling constant. At 300 K a quadrupole coupling constant of 256±5 kHz and an asymmetry parameter of 0.164 ± 0.003 were obtained. The temperature dependence of the quadrupole coupling constant was investigated. Ab initio calculation of the deuterium quadrupole coupling in liquid waterRolf Eggenberger, Stefan Gerber, Hanspeter Huber, Debra Searles, and Marc Welker

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The deuterium quadrupole coupling constant and asymmetry parameter in heavy water were determined using ab initio SCF calculations. Snapshots from a molecular dynamics simulation were used to give liquid water cluster configurations and the influence of simulation parameters on the quadrupole coupling constant was investigated. The electronic potential model and the number of molecules in the molecular dynamics simulation and the pressure of the system were found to have only a small influence on the quadrupole coupling constant. The average value of the quadrupole coupling constant at room temperature, corrected for the known deficiency of the ab initio calculation in the gas phase, yields a quadrupole coupling constant of 253 kHz, in perfect agreement with the most recent experiments. The oxygen-deuterium bond lengths in ice Ih, ice 11, and ice IX were determined using experimental quadrupole coupling constants and a model equation. An averaged bond length of 98.9 pm was obtained for the Ih form, which is approximately 2 pm shorter than that determined by neutron diffraction studies, whereas the bond lengths for the four deuterium sites in ice I1 and the three sites in ice IX are in fair agreement with experiment. 0 1993 by John Wiley & Sons, Inc.