ELECTRONIC TRANSITIONS IN α-FE2O3: THEORETICAL MODELS AND LIMITATIONS. Addressing electronic transitions of hematite (α-Fe2O3) is still considered a topic in active debate, even though it is one of the most widely used compounds from ancient times to the present and also one of the most extensively investigated iron oxides. In this review, a general analysis of the approaches and theoretical models which had been used to explain the electronic absorption spectrum of α-Fe2O3, from the frst proposal presented by Tandon and Gupta (1970) to the more recent results obtained by quantum mechanical calculations, is presented. The analysis of the already published studies is made pointing out the main factors that must be considered to allow a more reliable understanding of the UV-Vis-NIR spectra of α-Fe2O3. Furthermore, controversies in the calculated results are discussed, analysing the suitability of each of the approaches used. Reasons for differences observed in the experimental data reported in the literature are also discussed.

The preservation of Cultural Heritage is undoubtedly important for the society, and Conservation Science must dedicate itself to attempts to minimize the inherent processes of degradation to which cultural assets are susceptible. In this context, the evaluation of the chemical aspects of the composition of the objects and their relation with the environment where they are located are essential for the understanding of the decay signs observed, supporting the establishment of effective conservation strategies. These characteristics are demonstrated here by vibrational spectroscopy, scanning electron microscopy and microbiological analysis of efflorescences observed in two types of paintings: a tempera on canvas painting ("Barco com bandeirinhas e pássaros", Alfredo Volpi, 1955) and an oil mural painting of the Throne Room of the National Palace of Mafra (18th-19th century, Mafra, Portugal). The challenges involved in the investigation of the efflorescences are demonstrated in both cases, suggesting the occurrence of degradation processes of different origins: in Alfredo Volpi's tempera on canvas painting, the migration of substances from the preparation layer to the surface of the pictorial layer and microbiological colonization; and in the mural painting the migration of calcium salts from the constituent materials of plaster and of neoformation, besides associated microbiological colonization.