Anomalous temperature dependence of the experimental x-ray structure factor of supercooled water

The structural changes of water upon deep supercooling were studied through wide-angle x-ray scattering at SwissFEL. The experimental setup had a momentum transfer range of 4.5 angstrom(-1), which covered the principal doublet of the x-ray structure factor of water. The oxygen-oxygen structure factor was obtained for temperatures down to 228.5 +/- 0.6 K. Similar to previous studies, the second diffraction peak increased strongly in amplitude as the structural change accelerated toward a local tetrahedral structure upon deep supercooling. We also observed an anomalous trend for the second peak position of the oxygen-oxygen structure factor (q(2)). We found that q(2) exhibits an unprecedented positive partial derivative with respect to temperature for temperatures below 236 K. Based on Fourier inversion of our experimental data combined with reference data, we propose that the anomalous q(2) shift originates from that a repeat spacing in the tetrahedral network, associated with all peaks in the oxygen-oxygen pair-correlation function, gives rise to a less dense local ordering that resembles that of low-density amorphous ice. The findings are consistent with that liquid water consists of a pentamer-based hydrogen-bonded network with low density upon deep supercooling. (C) 2021 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).

Automated summary

The study investigated the structural changes of water upon deep supercooling using wide-angle x-ray scattering at SwissFEL. It found that the oxygen-oxygen structure factor exhibited a strong increase in amplitude for the second diffraction peak, while q(2) showed an unprecedented positive partial derivative with respect to temperature below 236 K, indicating a less dense local ordering. The findings suggest that liquid water forms a pentamer-based hydrogen-bonded network with low density under deep supercooling conditions.