Structure and bonding in silver halides. A quantum chemical study of the monomers: Ag(2)X, AgX, AgX(2), and AgX(3) (X = F, Cl, Br, I)

• Published in: Journal of the American Chemical Society 2005-06, Vol.127 (22), p.8133-8145
• Main Authors: Müller-Rösing, Hans-Christian, Schulz, Axel, Hargittai, Magdolna
• Format: Article
• Language: English
• ISSN: 0002-7863

The molecular structure of all silver halide monomers, Ag(2)X, AgX, AgX(2), and AgX(3), (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 Ag(2)X silver subhalides has C(2)(v)() symmetry, and the molecules can be best described as [Ag(2)](+)X(-). Silver dihalides are linear molecules; AgF(2) has a (2)Sigma(g) ground state, while all of the other silver dihalides have a ground state of (2)Pi(g) 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 AgF(3) is a T-shaped structure with C(2)(v)() symmetry. For AgCl(3), AgBr(3), and AgI(3), 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 X(2) acting as donor and AgX as acceptor. Thus, except for AgF(3), in the other three silver trihalides, silver is not present in the formal oxidation state 3.