Tracking water dimers in ambient nanocapsules by vibrational spectroscopy

A Hwang, Rohit Chikkaraddy, D Grys, O Scherman*, J Baumberg*, B Nijis*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

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Abstract

Nanoconfined few-molecule water clusters are invaluable systems to study fundamental aspects of hydrogen bonding. Unfortunately, most experiments on water clusters must be performed at cryogenic temperatures. Probing water clusters in noncryogenic systems is however crucial to understand the behavior of confined water in atmospheric or biological settings, but such systems usually require either complex synthesis and/or introduce many confounding external bonds to the clusters. Here, we show that combining Raman spectroscopy with the molecular nanocapsule cucurbituril is a powerful technique to sequester and analyze water clusters in ambient conditions. We observe sharp peaks in vibrational spectra arising from a single rigid confined water dimer. The high resolution and rich information in these vibrational spectra allow us to track specific isotopic exchanges inside the water dimer, verified with density-functional theory and kinetic population modeling. We showcase the versatility of such molecular nanocapsules by tracking water cluster vibrations through systematic changes in confinement size, in temperatures up to 120° C, and in their chemical environment.
Original languageEnglish
Article numbere2212497119
Number of pages8
JournalProceedings of the National Academy of Sciences of the United States of America
Volume119
Issue number49
DOIs
Publication statusPublished - 1 Dec 2022

Keywords

  • water clusters
  • water dimer
  • vibrational spectroscopy
  • cucurbituril

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