Infrared spectroscopy of hydrated halide ion clusters

Mitchio Okumura, Jong-Ho Choi, Keith T. Kuwata, Yi Bin Cao, Bernd Michael Haas

Research output: Chapter in Book/Report/Conference proceedingConference contribution

7 Citations (Scopus)

Abstract

Clusters composed of solvated ions provide a valuable prototype system for studying molecular aspects of solvation. Vibrational spectroscopy can provide insight into how the solvent structure around an ion evolves with cluster size. We describe studies which illustrate the effects of adding small numbers of solvent molecules to anions. Halide ions are among the most ubiquitous and fundamental anions in aqueous chemistry. Recent calculations and photoelectron spectroscopy experiments suggest that hydrated halide ion clusters X -(H 2O) n have structures in which the anion binds to the surface of water clusters, rather than being surrounded by solvent water molecules (so-called interior states). We have observed infrared spectra for a series of solvated chloride ions which can be assigned with the aid of ab initio calculations. We find that for the chloride ion the water molecules tend to associate, but that water-water hydrogen bonds are not necessarily formed at the smallest size. Our results suggest the importance of entropic factors in these floppy clusters. Evidence is also found for a possible transition to liquid-like structures at a critical cluster size.

Original languageEnglish
Title of host publicationProceedings of SPIE - The International Society for Optical Engineering
EditorsJohn W. Hepburn
Pages147-156
Number of pages10
Volume2548
Publication statusPublished - 1995 Dec 1
Externally publishedYes
EventLaser Techniques for State-Selected and State-to-State Chemistry III - San Diego, CA, USA
Duration: 1995 Jul 121995 Jul 14

Other

OtherLaser Techniques for State-Selected and State-to-State Chemistry III
CitySan Diego, CA, USA
Period95/7/1295/7/14

Fingerprint

halides
Infrared spectroscopy
infrared spectroscopy
Ions
ions
Negative ions
water
Water
anions
Molecules
chlorides
molecules
Vibrational spectroscopy
Solvation
Photoelectron spectroscopy
spectroscopy
solvation
Hydrogen bonds
infrared spectra
prototypes

ASJC Scopus subject areas

  • Electrical and Electronic Engineering
  • Condensed Matter Physics

Cite this

Okumura, M., Choi, J-H., Kuwata, K. T., Cao, Y. B., & Haas, B. M. (1995). Infrared spectroscopy of hydrated halide ion clusters. In J. W. Hepburn (Ed.), Proceedings of SPIE - The International Society for Optical Engineering (Vol. 2548, pp. 147-156)

Infrared spectroscopy of hydrated halide ion clusters. / Okumura, Mitchio; Choi, Jong-Ho; Kuwata, Keith T.; Cao, Yi Bin; Haas, Bernd Michael.

Proceedings of SPIE - The International Society for Optical Engineering. ed. / John W. Hepburn. Vol. 2548 1995. p. 147-156.

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Okumura, M, Choi, J-H, Kuwata, KT, Cao, YB & Haas, BM 1995, Infrared spectroscopy of hydrated halide ion clusters. in JW Hepburn (ed.), Proceedings of SPIE - The International Society for Optical Engineering. vol. 2548, pp. 147-156, Laser Techniques for State-Selected and State-to-State Chemistry III, San Diego, CA, USA, 95/7/12.
Okumura M, Choi J-H, Kuwata KT, Cao YB, Haas BM. Infrared spectroscopy of hydrated halide ion clusters. In Hepburn JW, editor, Proceedings of SPIE - The International Society for Optical Engineering. Vol. 2548. 1995. p. 147-156
Okumura, Mitchio ; Choi, Jong-Ho ; Kuwata, Keith T. ; Cao, Yi Bin ; Haas, Bernd Michael. / Infrared spectroscopy of hydrated halide ion clusters. Proceedings of SPIE - The International Society for Optical Engineering. editor / John W. Hepburn. Vol. 2548 1995. pp. 147-156
@inproceedings{6ba2d08f220348ff9db4fef652d5b2e9,
title = "Infrared spectroscopy of hydrated halide ion clusters",
abstract = "Clusters composed of solvated ions provide a valuable prototype system for studying molecular aspects of solvation. Vibrational spectroscopy can provide insight into how the solvent structure around an ion evolves with cluster size. We describe studies which illustrate the effects of adding small numbers of solvent molecules to anions. Halide ions are among the most ubiquitous and fundamental anions in aqueous chemistry. Recent calculations and photoelectron spectroscopy experiments suggest that hydrated halide ion clusters X -(H 2O) n have structures in which the anion binds to the surface of water clusters, rather than being surrounded by solvent water molecules (so-called interior states). We have observed infrared spectra for a series of solvated chloride ions which can be assigned with the aid of ab initio calculations. We find that for the chloride ion the water molecules tend to associate, but that water-water hydrogen bonds are not necessarily formed at the smallest size. Our results suggest the importance of entropic factors in these floppy clusters. Evidence is also found for a possible transition to liquid-like structures at a critical cluster size.",
author = "Mitchio Okumura and Jong-Ho Choi and Kuwata, {Keith T.} and Cao, {Yi Bin} and Haas, {Bernd Michael}",
year = "1995",
month = "12",
day = "1",
language = "English",
isbn = "0819419079",
volume = "2548",
pages = "147--156",
editor = "Hepburn, {John W.}",
booktitle = "Proceedings of SPIE - The International Society for Optical Engineering",

}

TY - GEN

T1 - Infrared spectroscopy of hydrated halide ion clusters

AU - Okumura, Mitchio

AU - Choi, Jong-Ho

AU - Kuwata, Keith T.

AU - Cao, Yi Bin

AU - Haas, Bernd Michael

PY - 1995/12/1

Y1 - 1995/12/1

N2 - Clusters composed of solvated ions provide a valuable prototype system for studying molecular aspects of solvation. Vibrational spectroscopy can provide insight into how the solvent structure around an ion evolves with cluster size. We describe studies which illustrate the effects of adding small numbers of solvent molecules to anions. Halide ions are among the most ubiquitous and fundamental anions in aqueous chemistry. Recent calculations and photoelectron spectroscopy experiments suggest that hydrated halide ion clusters X -(H 2O) n have structures in which the anion binds to the surface of water clusters, rather than being surrounded by solvent water molecules (so-called interior states). We have observed infrared spectra for a series of solvated chloride ions which can be assigned with the aid of ab initio calculations. We find that for the chloride ion the water molecules tend to associate, but that water-water hydrogen bonds are not necessarily formed at the smallest size. Our results suggest the importance of entropic factors in these floppy clusters. Evidence is also found for a possible transition to liquid-like structures at a critical cluster size.

AB - Clusters composed of solvated ions provide a valuable prototype system for studying molecular aspects of solvation. Vibrational spectroscopy can provide insight into how the solvent structure around an ion evolves with cluster size. We describe studies which illustrate the effects of adding small numbers of solvent molecules to anions. Halide ions are among the most ubiquitous and fundamental anions in aqueous chemistry. Recent calculations and photoelectron spectroscopy experiments suggest that hydrated halide ion clusters X -(H 2O) n have structures in which the anion binds to the surface of water clusters, rather than being surrounded by solvent water molecules (so-called interior states). We have observed infrared spectra for a series of solvated chloride ions which can be assigned with the aid of ab initio calculations. We find that for the chloride ion the water molecules tend to associate, but that water-water hydrogen bonds are not necessarily formed at the smallest size. Our results suggest the importance of entropic factors in these floppy clusters. Evidence is also found for a possible transition to liquid-like structures at a critical cluster size.

UR - http://www.scopus.com/inward/record.url?scp=0029479655&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0029479655&partnerID=8YFLogxK

M3 - Conference contribution

AN - SCOPUS:0029479655

SN - 0819419079

SN - 9780819419071

VL - 2548

SP - 147

EP - 156

BT - Proceedings of SPIE - The International Society for Optical Engineering

A2 - Hepburn, John W.

ER -