Abstract: The study of chemical factors that influence pigment coloring is a field of fundamental interest that is still dominated by many uncertainties. In this Article, we investigate, by means of ab initio calculations, the origin of the unusual bright blue color displayed by historical Egyptian Blue (CaCuSi4O10) and Han Blue (BaCuSi4O10) pigments that is surprisingly not found in other compounds like BaCuSi2O6 or CaCuO2 containing the same CuO46– chromophore. We show that the differences in hue between these systems are controlled by a large red-shift (up to 7100 cm–1) produced by an electrostatic field created by a lattice over the CuO46– chromophore from the energy of the 3z2-r2 ? x2-y2 transition, a nonlocal phenomenon widely ignored in the realm of transition metal chemistry and strongly dependent upon the crystal structure. Along this line, we demonstrate that, although SiO44– units are not involved in the chromophore itself, the introduction of sand to create CaCuSi4O10 plays a key role in obtaining the characteristic hue of the Egyptian Blue pigment. The results presented here demonstrate the opportunity for tuning the properties of a given chromophore by modifying the structure of the insulating lattice where it is located.

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