Coordination structures of the silver ion: infrared photodissociation spectroscopy of Ag(+)(NH(3))(n) (n = 3-8).

Infrared (IR) spectra are measured for Ag(+)(NH(3))(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 NH(3), indicating that every NH(3) molecule is coordinated individually to Ag(+). For n >or= 5, the occupation of the second shell is evidenced by lower-frequency features characteristic of hydrogen bonding between NH(3) molecules.

Coordination and solvation of copper ion: infrared photodissociation spectroscopy of Cu(+)(NH(3))(n) (n = 3-8).

Coordination and solvation structures of the Cu(+)(NH(3))(n) ions with n = 3-8 are studied by infrared photodissociation spectroscopy in the NH-stretch region with the aid of density functional theory calculations. Hydrogen bonding between NH(3) molecules is absent for n = 3, indicating that all NH(3) molecules are bonded directly to Cu(+) in a tri-coordinated form. The first sign of hydrogen bonding is detected at n = 4 through frequency reduction and intensity enhancement of the infrared transitions, implying that at least one NH(3) molecule is placed in the second solvation shell.

Infrared spectroscopy of Cu+(H2O)(n) and Ag+(H2O)(n): coordination and solvation of noble-metal ions.

M(+)(H(2)O)(n) and M(+)(H(2)O)(n)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.