Quantum-chemical calculations of a long proton wire. Application of a harmonic model to analysis of the structure of an ionic defect in a water chain with an excess proton.

Quantum-chemical calculations of molecular complexes (NH(3))(3)Zn(2+)...(H(2)O)(n)...NH(3) (C(n), n = 11, 16, 21, and 30) simulating a proton wire donor-water chain-acceptor were carried out. Earlier found periodicity in the length of the O-H bonds in water chain is explained within the framework of a one-component harmonic model. In complexes C(n), the geometry and electronic structure of ionic defect in water chain with an excess proton were studied. Calculations carried out at ab initio (B3LYP/6-31+G**) and semiempirical (PM3) levels of theory predict different patterns of distribution of the O-H bonds lengths and positive charge on the H-bond hydrogen atoms in the region of ionic defect. The obtained data show how a length of water chain and position of a protonated water link in the chain influence the ionic defect structure. To describe the observed structures of ionic defect, the harmonic model was used and the role of parameters of the H-bonded chain was investigated. The performed analysis explains different mechanisms (concerted and stepwise) of proton transfer along the H-bonded chain derived from ab initio and semiempirical calculation schemes.