Atypical water lattices and their possible relevance to the amorphous ices: A density functional study

摘要

Of the fifteen known crystalline forms of ice, eleven consist of a single topologically connected hydrogen bond network with four H-bonds at every O. The other four, Ices VI–VIII and XV, consist of two topologically connected networks, each with four H-bonds at every O. The networks interpenetrate but do not share H-bonds. This article presents two new periodic water lattice families whose topological connectivity is “atypical”: they consist of many two-dimensional layers that share no H-bonds. Layers are held together only by dispersion forces. Within each layer there are still four H-bonds at each O. Called “Hexagonal Bilayer Water” (HBW) and “Pleated Sheet Water” (PSW), they have computed densities of about 1.1 g/mL and 1.3 g/mL respectively, and nearest neighbor O-coordination is 4.5 to 5.5 and 6 to 8 respectively. Using density functional theory (BLYP-D/TZVP), various proton ordered forms of HBW and PSW are optimized and categorized. There are simple pathways connecting Ice-Ih to HBW and HBW to PSW. Their computed properties suggest similarities to the high density and very high density amorphous ices (HDA and VHDA) respectively. It is unknown whether HDA, VHDA, and Low Density Amorphous Ice (LDA) are fully disordered glasses down to the molecular level, or whether there is some short-range local order. Based on estimated radial distribution functions (RDFs), one proton ordered form of HBW matches HDA best. The idea is explored that HDA could contain islands with this underlying structure, and likewise, that VHDA could contain regions of PSW. A “microlattice model version 1” (MLM1) is presented as a device to compare key experimental data on the amorphous ices with these atypical structures and with a microlattice form of Ice-XI for LDA. Resemblances are found with the amorphs’ RDFs, densities, Raman spectra, and transition behaviors. There is not enough information in the static models to assign either a microlattice structure or a partial microlattice structure to any amorphous ice phase.