Stabilization energies polar

Many of the spinel-type compounds mentioned above do not have the normal structure in which A are in tetrahedral sites (t) and B are in octahedral sites (o) instead they adopt the inverse spinel structure in which half the B cations occupy the tetrahedral sites whilst the other half of the B cations and all the A cations are distributed on the octahedral sites, i.e. (B)t[AB]o04. The occupancy of the octahedral sites may be random or ordered. Several factors influence whether a given spinel will adopt the normal or inverse structure, including (a) the relative sizes of A and B, (b) the Madelung constants for the normal and inverse structures, (c) ligand-field stabilization energies (p. 1131) of cations on tetrahedral and octahedral sites, and (d) polarization or covalency effects. ... 

When one places an electron into the donor molecule, the equilibrium fast polarization, which is purely electronic forms first. Being independent of the electron position, it is unimportant for the dynamics of electron transfer. Afterward the average slow polarization Pg, arises that corresponds to the initial (0 charge distribution (the electron in the donor). The interaction of the electron with this polarization stabilizes the electron state in the donor (with respect to that in the isolated donor molecule) (i.e., its energy level is lowered) (Fig. 34.1). At the same time, a given configuration of slow, inertial polarization destabilizes the electron state (vacant) in the acceptor (Fig. 34.1). Therefore, even for identical reactants, the electron energy levels in the donor and acceptor are different at the initial equilibrium value of slow polarization. 

Figure 1.14 Increasing solvent polarity stabilizes the zwitterionic ground state Or) of Rei-chardt s dye relative to the first excited state (n ), leading to an increase in the transition energy...

The total stabilization energy of a cluster rarely exceeds 25 kcal mol , i.e., a small fraction of a strong covalent bond energy (ca. 100 kcal mol ). Its partitioning into electrostatic, induction, and dispersion terms differs from cluster to cluster. In some cases, one particular energy term is dominant. More typically, many attractive terms contribute to the overall stabilization of non-covalent clusters, as it often happens to hydrogen-bonded complexes. Nevertheless, the electrostatic interaction plays a dominant role, and in the case of polar subsystems. 

These experiments show that the more polar ionic forms seem to be favored in the matrix with respect to the neutral ones, as is expected from well known formulae for the stabilization energy of a system of charges in an apolar solvent. Their leading term,... 

Assembled in table 5.11 are the crystal field parameters derived from the spectra of several Cr3+-bearing minerals. For non-cubic minerals, the energies of bands and t)2 represent values averaged from the polarized absorption spectra. Crystal field stabilization energies calculated from band Dj, and corresponding to 1.2 x A0 (table 2.2), decrease in the order... 

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