Charge-transfer transitions

A complex may absorb radiation as a result of the transfer of an electron from the ligands into the d-orbitals of the central atom, or vice versa. In such charge-transfer transitions the electron moves through a considerable distance, which means that the transition dipole moment may be large and the absorption is correspondingly intense. This mode of chromophore activity is shown by the permanganate ion, MnO₄ −, and accounts for its intense violet colour (which arises from strong absorption within the range 420–700 nm). In this oxoanion, the electron migrates from an orbital that is largely confined to the O atom ligands to an orbital that is largely confined to the Mn atom. It is therefore an example of a ligand-to-metal charge-transfer transition (LMCT). The reverse migration, a metal-to-ligand charge-transfer transition (MLCT), can also occur. An example is the transfer of a d electron into the antibonding π orbitals of an aromatic ligand. The resulting excited state may have a very long lifetime if the electron is extensively delocalized over several aromatic rings, and such species can participate in photochemically induced redox reactions . The intensities of charge-transfer transitions are proportional to the square of the transition dipole moment, in the usual way. We can think of the transition moment as a measure of the distance moved by the electron as it migrates from metal to ligand or vice versa, with a large distance of migration corresponding to a large transition dipole moment and therefore a high intensity of absorption. However, because the integrand in the transition dipole is proportional to the product of the initial and final wavefunctions, it is zero unless the two wavefunctions have nonzero values in the same region of space. Therefore, although large distances of migration favour high intensities, the diminished overlap of the initial and final wavefunctions for large separations of metal and ligands favours low intensities (see Problem 14.17). We encounter similar considerations when we examine electron transfer reactions, which can be regarded as a special type of charge-transfer transition.

Fig. 14.17 In circularly polarized light, the electric field at different points along the direction of propagation rotates. The arrays of arrows in these illustrations show the view of the electric field when looking toward the oncoming ray: (a) right circularly polarized, (b) left-circularly polarized light.

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Working galvanic cells

Electrolysis

Experimental techniques

The rate laws

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Mechanisms of heterogeneous catalysis

Mobility on surfaces

The rate of desorption