A proposal for the structure of high- and low-density fluctuations in liquid water

Based on recent experimental data that can be interpreted as indicating the presence of specific structures in liquid water, we build and optimize two structural models which we compare with the available experimental data. To represent the proposed high-density liquid structures, we use a model consisting of chains of water molecules, and for low-density liquid, we investigate fused dodecahedra as templates for tetrahedral fluctuations. The computed infrared spectra of the models are in very good agreement with the extracted experimental spectra for the two components, while the extracted structures from molecular dynamics (MD) simulations give spectra that are intermediate between the experimentally derived spectra. Computed x-ray absorption and emission spectra as well as the O–O radial distribution functions of the proposed structures are not contradicted by experiment. The stability of the proposed dodecahedral template structures is investigated in MD simulations by seeding the starting structure, and remnants found to persist on an ∼30 ps time scale. We discuss the possible significance of such seeds in simulations and whether they can be viable candidates as templates for structural fluctuations below the compressibility minimum of liquid water.