The End of Ice I

11 July 2019, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The appearance of ice I in the smallest possible clusters and the nature of its phase coexistence with liquid water could not thus far be unravelled. The experimental and theoretical infrared spectroscopic and free energy results of this work show the emergence of the characteristic hydrogen bonding pattern of ice I in clusters containing only around 90 water molecules. The onset of crystallization is accompanied by an increase of surface oscillator intensity with decreasing surface to volume ratio, a new spectral indicator of nanoscale crystallinity of water. In the size range from 90 to 150 water molecules, we observe mixtures of largely crystalline and purely amorphous clusters. Our analysis suggests that the liquid-ice I transition in clusters loses its sharp first-order character at the end of the crystalline size regime and occurs over a range of temperatures through heterophasic oscillations in time, a process without analog in bulk water.


infrared spectroscopy
molecular dynamics
computational spectroscopy
many-body effects
data-driven models
coarse graining
free energies

Supplementary materials

The end of ice I si


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