Transient absorption study on Red Vermilion darkening in presence of chlorine ions and after UV exposure

[Display omitted] •Vermilion darkening process studied with a phase transformation.•Transient absorption spectroscopy applied to pigments degradation.•Cinnabar degradation is accelerated in presence of chlorine ions. The application of no destructive techniques in the field of Cultural Heritage is becoming fundamental to understanding degradation phenomena. In this study, Transient Absorption (TA) spectroscopy was exploited to explain the process which causes the darkening of Red Vermilion, a famous pigment known also as cinnabar. The optical properties involved in the process are studied in pure HgS and chlorine doped HgS samples, before and after exposure to UV light (365 nm). The study was carried out with particular attention on the ground state bleaching signals, directly connected to the formation of intra-gap trap levels responsible for the pigment degradation. First derivative reflectance spectra reveal the presence of these defectivities, while the analysis of Tauc plots from Kubelka Munk function confirms the reduction of energy band gap due to UV exposure. With the help of Density Functional calculations, we simulated the role of S vacancies in producing a defective alpha-phase, the consequent reduction of the energy band gap and, finally, the progressive phase transformation to the cubic metacinnabar. Transient Absorption turns out to be an important tool of diagnosis about the conservation state of pigments applied in the field of Cultural Heritage.