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IR Spectroscopy of the Cesium Iodide–Water Complex

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journal contribution
posted on 03.09.2020, 11:15 by Julia A Davies, Martin Mugglestone, Shengfu Yang, Andrew M Ellis
There has been much interest in I–(H2O) as a simple model for a hydrated iodide ion. Here we explore how this fundamental ion–solvent interaction is modified by the presence of a counterion, specifically Cs+. This has been achieved by forming the CsI(H2O) complex in superfluid helium nanodroplets and then probing this system using infrared spectroscopy. The complex retains the ionic hydrogen bond between the I– and a water OH group seen in I–(H2O), but the Cs+ ion substantially alters the anion–water interaction through formation of a cyclic Cs+–O–H–I– bonding motif. As with I–(H2O), the OH stretching band derived from the hydrogen-bonded OH group shows substructure, splitting into a clear doublet. However, in contrast to I–(H2O), where a tunneling splitting arising from hydrogen atom exchange plays a role, the doublet we observe is attributed solely to an anharmonic vibrational coupling effect.

History

Citation

J. Phys. Chem. A 2020, 124, 32, 6528–6535

Author affiliation

Department of Chemistry

Version

AM (Accepted Manuscript)

Published in

The Journal of Physical Chemistry A

Volume

124

Issue

32

Pagination

6528-6535

Publisher

American Chemical Society (ACS)

issn

1089-5639

eissn

1520-5215

Acceptance date

20/07/2020

Copyright date

2020

Available date

20/07/2021

Language

en

Publisher version

https://pubs.acs.org/doi/10.1021/acs.jpca.0c05224

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