Abstract
A simple binding-site model is developed to describe the behavior and optical response of binuclear mixed-valent metal complexes in mixed solvents. A free energy expression is constructed, including energy terms due to electron delocalization, to solvent molecules in the first solvation shell, and to interactions between solvent molecules, both in the bulk and in the first shell. An entropy term includes effects of parititioning the solvent species between bulk solvent and solvation shells. Minimization of the free energy yields an equilibrium condition; the resulting equations are precisely those of the two-sublattice model for magnetism. Conditions for symmetric solvation or for asymmetric solvation (with a corresponding blue shift in the intervalence-transfer absorption band) are developed, as a function of solvent composition and temperature. A phase diagram is given; at low temperatures, asymmetric solvation will almost always occur.
| Original language | English |
|---|---|
| Pages (from-to) | 5065-5070 |
| Number of pages | 6 |
| Journal | Journal of Physical Chemistry |
| Volume | 93 |
| Issue number | 13 |
| Publication status | Published - 1989 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
Cite this
Selective solvation effects on mixed-valency species in mixed solvents. / Katriel, J.; Ratner, Mark A.
In: Journal of Physical Chemistry, Vol. 93, No. 13, 1989, p. 5065-5070.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Selective solvation effects on mixed-valency species in mixed solvents
AU - Katriel, J.
AU - Ratner, Mark A
PY - 1989
Y1 - 1989
N2 - A simple binding-site model is developed to describe the behavior and optical response of binuclear mixed-valent metal complexes in mixed solvents. A free energy expression is constructed, including energy terms due to electron delocalization, to solvent molecules in the first solvation shell, and to interactions between solvent molecules, both in the bulk and in the first shell. An entropy term includes effects of parititioning the solvent species between bulk solvent and solvation shells. Minimization of the free energy yields an equilibrium condition; the resulting equations are precisely those of the two-sublattice model for magnetism. Conditions for symmetric solvation or for asymmetric solvation (with a corresponding blue shift in the intervalence-transfer absorption band) are developed, as a function of solvent composition and temperature. A phase diagram is given; at low temperatures, asymmetric solvation will almost always occur.
AB - A simple binding-site model is developed to describe the behavior and optical response of binuclear mixed-valent metal complexes in mixed solvents. A free energy expression is constructed, including energy terms due to electron delocalization, to solvent molecules in the first solvation shell, and to interactions between solvent molecules, both in the bulk and in the first shell. An entropy term includes effects of parititioning the solvent species between bulk solvent and solvation shells. Minimization of the free energy yields an equilibrium condition; the resulting equations are precisely those of the two-sublattice model for magnetism. Conditions for symmetric solvation or for asymmetric solvation (with a corresponding blue shift in the intervalence-transfer absorption band) are developed, as a function of solvent composition and temperature. A phase diagram is given; at low temperatures, asymmetric solvation will almost always occur.
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UR - http://www.scopus.com/inward/citedby.url?scp=11544271153&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:11544271153
VL - 93
SP - 5065
EP - 5070
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
SN - 0022-3654
IS - 13
ER -