Coordination structures of the silver ion

Infrared photodissociation spectroscopy of Ag+(NH3)n (n = 3-8)

Kazuya Inoue, Kazuhiko Ohashi, Takuro Iino, Jun Sasaki, Ken Judai, Nobuyuki Nishi, Hiroshi Sekiya

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Infrared (IR) spectra are measured for Ag+(NH3) n with n = 3-8 in the NH-stretch region using photodissociation spectroscopy. The spectra of n = 3 and 4 exhibit absorption features only near the frequencies of the isolated NH3, indicating that every NH 3 molecule is coordinated individually to Ag+. For n ≥ 5, the occupation of the second shell is evidenced by lower-frequency features characteristic of hydrogen bonding between NH3 molecules. Density functional theory and MP2 calculations are carried out in support of the experiments. A detailed comparison of the experimental and theoretical IR spectra reveals the preference for a tetrahedral coordination in the n = 5 and 6 ions. Likewise, most of the features observed in the spectra of n = 7 and 8 can be assigned to isomers containing a tetrahedrally coordinated inner shell as the basic structural motif. These results signify that the ammonia-solvated Ag+ ion has a propensity toward a coordination number of four and the resulting tetrahedral Ag+(NH3)4 complex forms the central core of further solvation process.

Original languageEnglish
Pages (from-to)3052-3062
Number of pages11
JournalPhysical Chemistry Chemical Physics
Volume10
Issue number21
DOIs
Publication statusPublished - 2008

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Photodissociation
Silver
photodissociation
infrared spectra
silver
Shells (structures)
Spectroscopy
Ions
Infrared radiation
Molecules
Solvation
coordination number
Ammonia
Isomers
occupation
spectroscopy
Density functional theory
solvation
molecules
ammonia

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Coordination structures of the silver ion : Infrared photodissociation spectroscopy of Ag+(NH3)n (n = 3-8). / Inoue, Kazuya; Ohashi, Kazuhiko; Iino, Takuro; Sasaki, Jun; Judai, Ken; Nishi, Nobuyuki; Sekiya, Hiroshi.

In: Physical Chemistry Chemical Physics, Vol. 10, No. 21, 2008, p. 3052-3062.

Research output: Contribution to journalArticle

Inoue, Kazuya ; Ohashi, Kazuhiko ; Iino, Takuro ; Sasaki, Jun ; Judai, Ken ; Nishi, Nobuyuki ; Sekiya, Hiroshi. / Coordination structures of the silver ion : Infrared photodissociation spectroscopy of Ag+(NH3)n (n = 3-8). In: Physical Chemistry Chemical Physics. 2008 ; Vol. 10, No. 21. pp. 3052-3062.
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