Vibrational spectroscopy of the Cl-(H2O)n anionic clusters, n = 1-5

Jong Ho Choi; Keith T. Kuwata; Yi Bin Cao; Mitchio Okumura

doi:10.1021/jp9729425

Vibrational spectroscopy of the Cl^-(H₂O)_n anionic clusters, n = 1-5

Jong Ho Choi, Keith T. Kuwata, Yi Bin Cao, Mitchio Okumura

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Abstract

The hydrogen-bonded and free OH stretch modes of Cl^-(H₂O)_n (n = 1-5) have been observed by vibrational predissociation spectroscopy in the 2.6-3.2 μm region. Besides demonstrating that all clusters form strong ionic hydrogen bonds, the spectra provide clear evidence of water-water hydrogen-bonding networks in n = 4 and n = 5, with the broad spectrum of n = 5 resembling that of large neutral water clusters. No water-water hydrogen bonding is seen in n = 2 and n = 3, but these clusters appear to be solvated asymmetrically. While the data suggest that Cl^- ion is solvated on the surface of water clusters, there are discrepancies between the observed spectra and ab initio predictions. This disagreement may stem from either zero-point motion or high cluster temperature, which tend to disrupt hydrogen bonding among the waters.

Original language	English
Pages (from-to)	503-507
Number of pages	5
Journal	Journal of Physical Chemistry A
Volume	102
Issue number	3
DOIs	https://doi.org/10.1021/jp9729425
Publication status	Published - 1998 Jan 1

ASJC Scopus subject areas

Physical and Theoretical Chemistry

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title = "Vibrational spectroscopy of the Cl-(H2O)n anionic clusters, n = 1-5",

abstract = "The hydrogen-bonded and free OH stretch modes of Cl-(H2O)n (n = 1-5) have been observed by vibrational predissociation spectroscopy in the 2.6-3.2 μm region. Besides demonstrating that all clusters form strong ionic hydrogen bonds, the spectra provide clear evidence of water-water hydrogen-bonding networks in n = 4 and n = 5, with the broad spectrum of n = 5 resembling that of large neutral water clusters. No water-water hydrogen bonding is seen in n = 2 and n = 3, but these clusters appear to be solvated asymmetrically. While the data suggest that Cl- ion is solvated on the surface of water clusters, there are discrepancies between the observed spectra and ab initio predictions. This disagreement may stem from either zero-point motion or high cluster temperature, which tend to disrupt hydrogen bonding among the waters.",

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T1 - Vibrational spectroscopy of the Cl-(H2O)n anionic clusters, n = 1-5

AU - Choi, Jong Ho

AU - Kuwata, Keith T.

AU - Cao, Yi Bin

AU - Okumura, Mitchio

PY - 1998/1/1

Y1 - 1998/1/1

N2 - The hydrogen-bonded and free OH stretch modes of Cl-(H2O)n (n = 1-5) have been observed by vibrational predissociation spectroscopy in the 2.6-3.2 μm region. Besides demonstrating that all clusters form strong ionic hydrogen bonds, the spectra provide clear evidence of water-water hydrogen-bonding networks in n = 4 and n = 5, with the broad spectrum of n = 5 resembling that of large neutral water clusters. No water-water hydrogen bonding is seen in n = 2 and n = 3, but these clusters appear to be solvated asymmetrically. While the data suggest that Cl- ion is solvated on the surface of water clusters, there are discrepancies between the observed spectra and ab initio predictions. This disagreement may stem from either zero-point motion or high cluster temperature, which tend to disrupt hydrogen bonding among the waters.

AB - The hydrogen-bonded and free OH stretch modes of Cl-(H2O)n (n = 1-5) have been observed by vibrational predissociation spectroscopy in the 2.6-3.2 μm region. Besides demonstrating that all clusters form strong ionic hydrogen bonds, the spectra provide clear evidence of water-water hydrogen-bonding networks in n = 4 and n = 5, with the broad spectrum of n = 5 resembling that of large neutral water clusters. No water-water hydrogen bonding is seen in n = 2 and n = 3, but these clusters appear to be solvated asymmetrically. While the data suggest that Cl- ion is solvated on the surface of water clusters, there are discrepancies between the observed spectra and ab initio predictions. This disagreement may stem from either zero-point motion or high cluster temperature, which tend to disrupt hydrogen bonding among the waters.

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Vibrational spectroscopy of the Cl^-(H₂O)_n anionic clusters, n = 1-5

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