The complex approximation is widely
used in the framework of the
Ligand Field Theory for explaining the optical properties of crystalline
coordination compounds. Here, we show that there are essential features
of these systems that cannot be understood with the usual approximation
that only considers an isolated complex at the correct equilibrium
geometry. We also show that a quantitative understanding of such optical
transitions cannot, in general, be reached unless the internal electric
field, E
R(r), created by the
whole crystal on active electrons confined in the complex, is also
taken into consideration. Seeking to prove the key role played by
this internal field, usually ignored in crystalline transition metal
compounds, we focus on the origin of the color displayed by the Egyptian
Blue pigment (CaCuSi4O10), the first ever synthesized
by humans. This pigment, together with Han Blue (BaCuSi4O10), are chosen as model systems because the anisotropic E
R(r) field produces huge shifts,
up to ∼0.9 eV, in their d–d transitions, which are unusual
compared to the majority of compounds containing the same square-planar
CuO4
6– chromophore. The relevance of
the internal field for explaining phenomena such as the distinct color
of ruby and emerald or the optical spectrum of CuF6
4– complexes in layered perovskites is also emphasized.