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 language | English |
|---|---|
| Title of host publication | Proceedings of SPIE - The International Society for Optical Engineering |
| Editors | John W. Hepburn |
| Pages | 147-156 |
| Number of pages | 10 |
| Volume | 2548 |
| Publication status | Published - 1995 Dec 1 |
| Externally published | Yes |
| Event | Laser Techniques for State-Selected and State-to-State Chemistry III - San Diego, CA, USA Duration: 1995 Jul 12 → 1995 Jul 14 |
Other
| Other | Laser Techniques for State-Selected and State-to-State Chemistry III |
|---|---|
| City | San Diego, CA, USA |
| Period | 95/7/12 → 95/7/14 |
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ASJC Scopus subject areas
- Electrical and Electronic Engineering
- Condensed Matter Physics
Cite this
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 proceeding › Conference contribution
}
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 -