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Insights Into Gas-Phase Structural Conformers of Hydrated Rubidium and Cesium Cations, M(+)(H2O)(n)Ar (M = Rb, Cs; N = 3-5), Using Infrared Photodissociation Spectroscopy

Insights Into Gas-Phase Structural Conformers of Hydrated Rubidium and Cesium Cations, M(+)(H2O)(n)Ar (M = Rb, Cs; N = 3-5), Using Infrared Photodissociation Spectroscopy

Haochen Ke, Christian van der Linde, James M Lisy

J Phys Chem A. 2014 Feb 27;118(8):1363-73.

PMID: 24502266

Abstract:

Infrared photodissociation (IRPD) spectra of M(+)(H2O)nAr (M = Rb, Cs; n = 3-5) with simultaneous monitoring of [Ar] and [Ar+H2O] fragmentation channels are reported. The comparison between the spectral features in the two channels and corresponding energy analysis provide spectral assignments of the stable structural conformers and insight into the competition between ion-water electrostatic and water-water hydrogen bonding interactions. Results show that as the level of hydration increases, the water-water interaction exhibits the tendency to dominate over the ion-water interaction. Cyclic water tetramer and water pentamer substructures appear in Cs(+)(H2O)4Ar and Cs(+)(H2O)5Ar systems, respectively. However, cyclic water tetramer and pentamer structures were not observed for Rb(+)(H2O)4Ar and Rb(+)(H2O)5Ar systems, respectively, due to the stronger influence of the rubidium ion-water electrostatic interaction. The energy analysis, including the available internal energy and the IR photon energy, helped provide an experimental estimate of water binding energies.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP12026050	Rubidium hydroxide hydrate		12026-05-0	Price

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