Polar solvent structural parameters from protonation equilibria of aliphatic and alicyclic diamines and from absorption bands of mixed-valence transition-metal complexes
✍ Scribed by A.A. Kornyshev; J. Ulstrup
- Publisher
- Elsevier Science
- Year
- 1986
- Tongue
- English
- Weight
- 671 KB
- Volume
- 126
- Category
- Article
- ISSN
- 0009-2614
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✦ Synopsis
We have applied non-local electrostatic theory in combination with a simple solute model to obtain solvent structural properties in terms of the short-range dielectric constant, Z, and the correlation length for the solvent polarization fluctuations, A. These parameters are fitted to experimental data for the free energy of interaction between protonated amino groups in dibasic amines and for intervalence band maxima of binuclear ruthenium complexes with bridge groups of varying length. The results show that non-local screening in the outer solvent, Z in the range 3.5-4 for water, and A = 2-3 A and 4 A for acetonitrile and water, respectively, provide good fits to the data, implying the significance of solvent structural effects for these phenomena.