Rapid water diffusion at cryogenic temperatures through an inchworm-like mechanism

TL;DR

This study reveals that water trimers can rapidly diffuse at cryogenic temperatures via an inchworm-like mechanism, involving subtle conformational changes that do not break hydrogen bonds, impacting understanding of ice formation and nanocluster behavior.

Contribution

The paper uncovers a novel low-temperature diffusion mechanism for water clusters, demonstrated through combined microscopy and theoretical calculations, advancing knowledge of molecular surface processes.

Findings

Water trimers diffuse at temperatures below 10 K.

Diffusion involves conformational changes without hydrogen bond breakage.

Mechanism resembles an inchworm-like motion.

Abstract

Water diffusion across the surfaces of materials is of importance to disparate processes such as water purification, ice formation, and more. Despite reports of rapid water diffusion on surfaces the molecular-level details of such processes remain unclear. Here, with scanning tunneling microscopy, we observe structural rearrangements and diffusion of water trimers at unexpectedly low temperatures (< 10 K) on a copper surface; temperatures at which water monomers or other clusters do not diffuse. Density functional theory calculations reveal a facile trimer diffusion process involving transformations between elongated and almost cyclic conformers in an inchworm-like manner. These subtle intermolecular reorientations maintain an optimal balance of hydrogen-bonding and water-surface interactions throughout the process. This work shows that the diffusion of hydrogen-bonded clusters can occur at exceedingly low temperatures without the need for hydrogen bond breakage or exchange; findings that will influence Ostwald ripening of ice nanoclusters and hydrogen bonded clusters in general.