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Issue 1, 2016
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Probing the microsolvation of a quaternary ion complex: gas phase vibrational spectroscopy of (NaSO4)2(H2O)n=0–6, 8

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Abstract

We report infrared multiple photon dissociation spectra of cryogenically-cooled (NaSO4)2(H2O)n dianions (n = 0–6, 8) in the spectral range of the sulfate stretching and bending modes (580–1750 cm−1). Characteristic absorption bands and structural trends are identified based on a comparison to harmonic spectra of minimum-energy structures. The bare quarternary complex (NaSO4)2 exhibits a C2h structure containing two fourfold-coordinated sodium cations in-between the two chelating sulfate dianions. Its stepwise solvation is driven by an interplay of SO42−–H2O and Na+–H2O interactions. The first water binds in a tridentate intersulfate-bridging fashion. The second and third water molecules bind to the sulfate groups at either end of the complex, which is followed by the onset of water hydrogen-bond network formation. In contrast to the binary ion pair, NaSO4, no clear evidence for the disruption of the quaternary ion complex upon microhydration is found up to n = 8, underlining its remarkable stability and suggesting that the formation of quaternary ion complexes plays a central role in the initial stages of prenucleation in aqueous Na2SO4 solutions.

Graphical abstract: Probing the microsolvation of a quaternary ion complex: gas phase vibrational spectroscopy of (NaSO4−)2(H2O)n=0–6, 8

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Article information


Submitted
25 Sep 2015
Accepted
17 Nov 2015
First published
18 Nov 2015

This article is Open Access

Phys. Chem. Chem. Phys., 2016,18, 267-277
Article type
Paper
Author version available

Probing the microsolvation of a quaternary ion complex: gas phase vibrational spectroscopy of (NaSO4)2(H2O)n=0–6, 8

T. Wende, N. Heine, T. I. Yacovitch, K. R. Asmis, D. M. Neumark and L. Jiang, Phys. Chem. Chem. Phys., 2016, 18, 267
DOI: 10.1039/C5CP05762K

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