Thermal conductivity of normal and deuterated water, crystalline ice, and amorphous ices

The effect of deuteration on the thermal conductivity κ of water, crystalline ice, and amorphous ices was studied using the pressure induced amorphization of hexagonal ice, ice Ih, to obtain the deuterated, D₂O, forms of low-density amorphous (LDA), high-density amorphous (HDA), and very-high density amorphous (VHDA) ices. Upon deuteration, κ of ice Ih decreases between 3% and 4% in the 100-270 K range at ambient pressure, but the effect diminishes on densification at 130 K and vanishes just prior to amorphization near 0.8 GPa. The unusual negative value of the isothermal density ρ dependence of κ for ice Ih, g = (d ln κ/d ln ρ) = -4.4, is less so for deuterated ice: g = -3.8. In the case of the amorphous ices and liquid water, κ of water decreases by 3.5% upon deuteration at ambient conditions, whereas κ of HDA and VHDA ices instead increases by up to 5% for pressures up to 1.2 GPa at 130 K, despite HDA's and VHDA's structural similarities with water. The results are consistent with significant heat transport by librational modes in amorphous ices as well as water, and that deuteration increases phonon-phonon scattering in crystalline ice. Heat transport by librational modes is more pronounced in D₂O than in H₂O at low temperatures due to a deuteration-induced redshift of librational mode frequencies. Moreover, the results show that κ of deuterated LDA ice is 4% larger than that of normal LDA at 130 K, and both forms display an unusual temperature dependence of κ, which is reminiscent of that for crystals (κ ∼ T ^-1), and a unique negative pressure dependence of κ, which likely is linked to local-order structural similarities to ice Ih.