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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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Wende,  Thorsten
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Heine,  Nadja
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Asmis,  Knut R.
Molecular Physics, Fritz Haber Institute, Max Planck Society;
Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig;
State Key Laboratory of Molecular Reaction Dynamics, Collaborative Innovation Center of Chemistry for Energy and Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences;

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Jiang,  Ling
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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c5cp05762k.pdf
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Citation

Wende, T., Heine, N., Yacovitch, T. I., Asmis, K. R., Neumark, D. M., & Jiang, L. (2016). Probing the microsolvation of a quaternary ion complex: gas phase vibrational spectroscopy of (NaSO4)2(H2O)n=0–6, 8. Physical Chemistry Chemical Physics, 18(1), 267-277. doi:10.1039/C5CP05762K.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0029-BD00-C
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.