skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Infrared spectroscopy of Cu{sup +}(H{sub 2}O){sub n} and Ag{sup +}(H{sub 2}O){sub n}: Coordination and solvation of noble-metal ions

Abstract

M{sup +}(H{sub 2}O){sub n} and M{sup +}(H{sub 2}O){sub n}{center_dot}Ar ions (M=Cu and Ag) are studied for exploring coordination and solvation structures of noble-metal ions. These species are produced in a laser-vaporization cluster source and probed with infrared (IR) photodissociation spectroscopy in the OH-stretch region using a triple quadrupole mass spectrometer. Density functional theory calculations are also carried out for analyzing the experimental IR spectra. Partially resolved rotational structure observed in the spectrum of Ag{sup +}(H{sub 2}O){sub 1}{center_dot}Ar indicates that the complex is quasilinear in an Ar-Ag{sup +}-O configuration with the H atoms symmetrically displaced off axis. The spectra of the Ar-tagged M{sup +}(H{sub 2}O){sub 2} are consistent with twofold coordination with a linear O-M{sup +}-O arrangement for these ions, which is stabilized by the s-d hybridization in M{sup +}. Hydrogen bonding between H{sub 2}O molecules is absent in Ag{sup +}(H{sub 2}O){sub 3}{center_dot}Ar but detected in Cu{sup +}(H{sub 2}O){sub 3}{center_dot}Ar through characteristic changes in the position and intensity of the OH-stretch transitions. The third H{sub 2}O attaches directly to Ag{sup +} in a tricoordinated form, while it occupies a hydrogen-bonding site in the second shell of the dicoordinated Cu{sup +}. The preference of the tricoordination is attributable to the inefficient 5s-4dmore » hybridization in Ag{sup +}, in contrast to the extensive 4s-3d hybridization in Cu{sup +} which retains the dicoordination. This is most likely because the s-d energy gap of Ag{sup +} is much larger than that of Cu{sup +}. The fourth H{sub 2}O occupies the second shells of the tricoordinated Ag{sup +} and the dicoordinated Cu{sup +}, as extensive hydrogen bonding is observed in M{sup +}(H{sub 2}O){sub 4}{center_dot}Ar. Interestingly, the Ag{sup +}(H{sub 2}O){sub 4}{center_dot}Ar ions adopt not only the tricoordinated form but also the dicoordinated forms, which are absent in Ag{sup +}(H{sub 2}O){sub 3}{center_dot}Ar but revived at n=4. Size dependent variations in the spectra of Cu{sup +}(H{sub 2}O){sub n} for n=5-7 provide evidence for the completion of the second shell at n=6, where the dicoordinated Cu{sup +}(H{sub 2}O){sub 2} subunit is surrounded by four H{sub 2}O molecules. The gas-phase coordination number of Cu{sup +} is 2 and the resulting linearly coordinated structure acts as the core of further solvation processes.« less

Authors:
; ; ; ; ;  [1];  [2];  [2]
  1. Department of Chemistry, Faculty of Sciences, Kyushu University, Hakozaki, Fukuoka 812-8581 (Japan)
  2. (Japan)
Publication Date:
OSTI Identifier:
20991268
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 126; Journal Issue: 19; Other Information: DOI: 10.1063/1.2730830; (c) 2007 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; ABSORPTION SPECTROSCOPY; CATIONS; COPPER COMPOUNDS; COPPER IONS; DENSITY FUNCTIONAL METHOD; DISSOCIATION; INFRARED SPECTRA; MASS SPECTROMETERS; MOLECULAR CLUSTERS; PHOTOLYSIS; SILVER COMPOUNDS; SILVER IONS; SOLVATION; WATER

Citation Formats

Iino, Takuro, Ohashi, Kazuhiko, Inoue, Kazuya, Judai, Ken, Nishi, Nobuyuki, Sekiya, Hiroshi, Institute for Molecular Science, Myodaiji, Okazaki 444-8585, and Department of Chemistry, Faculty of Sciences, Kyushu University, Hakozaki, Fukuoka 812-8581. Infrared spectroscopy of Cu{sup +}(H{sub 2}O){sub n} and Ag{sup +}(H{sub 2}O){sub n}: Coordination and solvation of noble-metal ions. United States: N. p., 2007. Web. doi:10.1063/1.2730830.
Iino, Takuro, Ohashi, Kazuhiko, Inoue, Kazuya, Judai, Ken, Nishi, Nobuyuki, Sekiya, Hiroshi, Institute for Molecular Science, Myodaiji, Okazaki 444-8585, & Department of Chemistry, Faculty of Sciences, Kyushu University, Hakozaki, Fukuoka 812-8581. Infrared spectroscopy of Cu{sup +}(H{sub 2}O){sub n} and Ag{sup +}(H{sub 2}O){sub n}: Coordination and solvation of noble-metal ions. United States. doi:10.1063/1.2730830.
Iino, Takuro, Ohashi, Kazuhiko, Inoue, Kazuya, Judai, Ken, Nishi, Nobuyuki, Sekiya, Hiroshi, Institute for Molecular Science, Myodaiji, Okazaki 444-8585, and Department of Chemistry, Faculty of Sciences, Kyushu University, Hakozaki, Fukuoka 812-8581. Mon . "Infrared spectroscopy of Cu{sup +}(H{sub 2}O){sub n} and Ag{sup +}(H{sub 2}O){sub n}: Coordination and solvation of noble-metal ions". United States. doi:10.1063/1.2730830.
@article{osti_20991268,
title = {Infrared spectroscopy of Cu{sup +}(H{sub 2}O){sub n} and Ag{sup +}(H{sub 2}O){sub n}: Coordination and solvation of noble-metal ions},
author = {Iino, Takuro and Ohashi, Kazuhiko and Inoue, Kazuya and Judai, Ken and Nishi, Nobuyuki and Sekiya, Hiroshi and Institute for Molecular Science, Myodaiji, Okazaki 444-8585 and Department of Chemistry, Faculty of Sciences, Kyushu University, Hakozaki, Fukuoka 812-8581},
abstractNote = {M{sup +}(H{sub 2}O){sub n} and M{sup +}(H{sub 2}O){sub n}{center_dot}Ar ions (M=Cu and Ag) are studied for exploring coordination and solvation structures of noble-metal ions. These species are produced in a laser-vaporization cluster source and probed with infrared (IR) photodissociation spectroscopy in the OH-stretch region using a triple quadrupole mass spectrometer. Density functional theory calculations are also carried out for analyzing the experimental IR spectra. Partially resolved rotational structure observed in the spectrum of Ag{sup +}(H{sub 2}O){sub 1}{center_dot}Ar indicates that the complex is quasilinear in an Ar-Ag{sup +}-O configuration with the H atoms symmetrically displaced off axis. The spectra of the Ar-tagged M{sup +}(H{sub 2}O){sub 2} are consistent with twofold coordination with a linear O-M{sup +}-O arrangement for these ions, which is stabilized by the s-d hybridization in M{sup +}. Hydrogen bonding between H{sub 2}O molecules is absent in Ag{sup +}(H{sub 2}O){sub 3}{center_dot}Ar but detected in Cu{sup +}(H{sub 2}O){sub 3}{center_dot}Ar through characteristic changes in the position and intensity of the OH-stretch transitions. The third H{sub 2}O attaches directly to Ag{sup +} in a tricoordinated form, while it occupies a hydrogen-bonding site in the second shell of the dicoordinated Cu{sup +}. The preference of the tricoordination is attributable to the inefficient 5s-4d hybridization in Ag{sup +}, in contrast to the extensive 4s-3d hybridization in Cu{sup +} which retains the dicoordination. This is most likely because the s-d energy gap of Ag{sup +} is much larger than that of Cu{sup +}. The fourth H{sub 2}O occupies the second shells of the tricoordinated Ag{sup +} and the dicoordinated Cu{sup +}, as extensive hydrogen bonding is observed in M{sup +}(H{sub 2}O){sub 4}{center_dot}Ar. Interestingly, the Ag{sup +}(H{sub 2}O){sub 4}{center_dot}Ar ions adopt not only the tricoordinated form but also the dicoordinated forms, which are absent in Ag{sup +}(H{sub 2}O){sub 3}{center_dot}Ar but revived at n=4. Size dependent variations in the spectra of Cu{sup +}(H{sub 2}O){sub n} for n=5-7 provide evidence for the completion of the second shell at n=6, where the dicoordinated Cu{sup +}(H{sub 2}O){sub 2} subunit is surrounded by four H{sub 2}O molecules. The gas-phase coordination number of Cu{sup +} is 2 and the resulting linearly coordinated structure acts as the core of further solvation processes.},
doi = {10.1063/1.2730830},
journal = {Journal of Chemical Physics},
number = 19,
volume = 126,
place = {United States},
year = {Mon May 21 00:00:00 EDT 2007},
month = {Mon May 21 00:00:00 EDT 2007}
}