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Tracking water dimers in ambient nanocapsules by vibrational spectroscopy.

Published version
Peer-reviewed

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Authors

Grys, David-Benjamin 

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.

Description

Keywords

cucurbituril, vibrational spectroscopy, water clusters, water dimer, Nanocapsules, Vibration, Water, Polymers, Spectrum Analysis, Raman

Journal Title

Proc Natl Acad Sci U S A

Conference Name

Journal ISSN

0027-8424
1091-6490

Volume Title

Publisher

Proceedings of the National Academy of Sciences
Sponsorship
Royal Society (URF\R1\211162)
European Commission Horizon 2020 (H2020) ERC (883703)
Engineering and Physical Sciences Research Council (EP/L027151/1)
Engineering and Physical Sciences Research Council (EP/R020965/1)
AH acknowledges funding from the Churchill Scholarship. BdN acknowledges support from the Royal Society (URF\R1\211162). JJB acknowledges funding support from ERC PICOFORCE (No. 883703), EPSRC EP/L027151/1 and EP/R020965/1.
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