Isotope quantum effects in water around the freezing point

We have measured the difference in electronic structure factors between liquid H 2 O and D 2 O at temperatures of 268 and 273 K with high energy x-ray diffraction. These are compared to our previously published data measured from 279 to 318 K . We find that the total structural isotope effect increases by a factor of 3.5 over the entire range, as the temperature is decreased. Structural isochoric temperature differential and isothermal density differential functions have been used to compare these data to a thermodynamic model based upon a simple offset in the state function. The model works well in describing the magnitude of the structural differences above ∼ 310 K , but fails at lower temperatures. The experimental results are discussed in light of several quantum molecular dynamics simulations and are in good qualitative agreement with recent temperature dependent, rotationally quantized rigid molecule simulations.