Details

Autor(en) / Beteiligte

• Müller-Rösing, Hans-Christian
• Schulz, Axel
• Hargittai, Magdolna

Titel

Structure and Bonding in Silver Halides. A Quantum Chemical Study of the Monomers:  Ag2X, AgX, AgX2, and AgX3 (X = F, Cl, Br, I)

Ist Teil von

• Journal of the American Chemical Society, 2005-06, Vol.127 (22), p.8133-8145

Ort / Verlag

Washington, DC: American Chemical Society

Erscheinungsjahr

2005

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The molecular structure of all silver halide monomers, Ag2X, AgX, AgX2, and AgX3, (X = F, Cl, Br, I), have been calculated at the B3LYP, MP2, and CCSD(T) levels of theory by using quasirelativistic pseudopotentials for all atoms except fluorine and chlorine. All silver monohalides are stable molecules, while the relative stabilities of the subhalides, dihalides, and trihalides considerably decrease toward the larger halogens. The ground-state structure of all Ag2X silver subhalides has C 2 v symmetry, and the molecules can be best described as [Ag2]+X-. Silver dihalides are linear molecules; AgF2 has a 2Σg ground state, while all of the other silver dihalides have a ground state of 2Πg symmetry. The potential energy surface (PES) of all silver trihalides has been investigated. Neither of these molecules has a D 3 h symmetric trigonal planar geometry, due to their Jahn−Teller distortion. The minimum energy structure of AgF3 is a T-shaped structure with C 2 v symmetry. For AgCl3, AgBr3, and AgI3, the global minimum is an L-shaped structure, which lies outside the Jahn−Teller PES. This structure can be considered as a donor−acceptor system, with X2 acting as donor and AgX as acceptor. Thus, except for AgF3, in the other three silver trihalides, silver is not present in the formal oxidation state 3.