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Coherence in disordered condensed matter. III: H + and OH − ionic conductance and proton transfer reactions in aqueous solutions
Author(s) -
ChatzidimitriouDreismann C. A.,
Brändas E. J.
Publication year - 1990
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560370206
Subject(s) - ionic bonding , delocalized electron , chemistry , aqueous solution , ion , proton , context (archaeology) , chemical physics , physics , quantum mechanics , paleontology , organic chemistry , biology
The physical context of the high ionic conductivity of the H + and OH − ions in aqueous solutions is considered. Quantum dynamical aspects of the mobility of these ions are investigated, especially within the framework of the complex scaling method ( CSM ). It is argued that the high ionic mobilities under consideration are due to quantum delocalization of the ions as well as mass interference of the H + ions with water protons. This effect is formally described with the aid of the coherent ‐ dissipative structures , which become spontaneously created in the solution owing to the thermal motion. In particular, (1) a novel connection between the proton transfer rate (as measured by NMR) and the mobilities of the considered ions (as determined by conductivity measurements) is derived. Additionally, (2) a relation connecting the activation energies of the above reaction rates with the ionic mobilities is found. The above relations contain no fitting parameters. Comparisons with experimental results is made, which also reveals the predictive power of the present CSM treatment in the field of microdynamical processes in condensed phases.