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Abstract Iron-titanium (Fe-Ti) charge transfer is mentioned in numerous articles as the source of the coloration of many natural minerals and some man-made materials, but no global review of this phenomenon has been provided so far. Iron and titanium are ubiquitous in nature and are often found in the same material as Fe2+ and Fe3+, and Ti4+ (more rarely Ti3+). When Fe and Ti ions are in close geometric proximity in an oxide or (alumino)silicate structure, charge transfer can occur between the two ions, even though their concentration might be below 100 ppm. This results in a variety of absorption features that contributes to the color of minerals. Adebate remains on the exact nature of Fe/Ti electronic transition, i.e. Fe2+ + Ti4+ → Fe3+ + Ti3+ or the reverse, but solving this issue is not within the scope of the present work. Ascertaining a metal-metal charge transfer is often not straightforward. This review compiles existing knowledge on Fe-Ti charge transfer in both crystalline and amorphous materials and identifies several key characteristics in more than 40 different materials. A charge transfer is associated with broad, intense, optical absorption bands that decrease in intensity at elevated temperatures. It is also strongly pleochroic in non-isotropic materials. Until now, Fe-Ti charge transfer transitions have been primarily described in the 2.25 to 3.1 eV range, corresponding to yellow to orange to brown colors, with notable exceptions such as blue sapphire or kyanite, and green andalusite. This review suggests that Fe-Ti charge transfer can occur across the entire visible spectrum, and the position of the absorption band correlates with the Fe-Ti nteratomic distance. This correlation highlights the presence of multiple crystallographic sites for both Fe and Ti in many oxides, leading to multiple Fe-Ti bands within these materials (e.g. sapphire, ilmenite, pseudobrookite). Finally, the use of metal-metal distances is suggested to differentiate this heteronuclear Fe-Ti charge transfer from the common homonuclear charge transfer Fe2+-Fe3+. 

Abstract The absorption of light by Fe/Ti and Fe/Fe intervalence charge transfer (IVCT) bands has previously been found in aluminum oxide and Al2SiO5 aluminosilicate minerals to decrease markedly at elevated temperatures. Given the abundance of iron at depth in the Earth, assessing the generality with which and extent to which IVCT mineral phases become more optically transparent at temperature than they are under ambient conditions has potentially significant implications for the modeling of mantle geophysical processes such as radiative conductivity. A broad experimental survey of the optical absorption spectra at elevated temperatures of various mixed valence iron minerals has been conducted. The minerals considered here are cordierite, chloritoid, lazulite, dumortierite, jeremejevite, beryl, osumilite, biotite (mica), pargasite (amphibole) and aegirine (pyroxene). All samples transiently lose significant Fe/Fe IVCT feature intensity at temperature. In beryl, osumilite, biotite, pargasite and aegirine, spin-allowed Fe2+d-d features also decrease in integral intensity at temperature; in all but beryl, the intensity loss is significant. This trend is consistent with d-d band enhancement via Fe2+/Fe3+ exchange coupling, which has not previously been identified in the majority of these minerals. It is contrasted against the behavior of ordinary spinallowed Fe2+d-d bands in non-IVCT minerals forsterite (olivine) and elbaite (tourmaline). The depletion of Fe/Fe IVCT and enhanced Fe2+d-d band intensity at elevated temperatures may both be important mechanisms by which iron-bearing mineral phases become more optically transparent under conditions at depth. 

Abstract Single-crystal optical spectra of corundum (Al2O3) and the Al2SiO5 polymorphs andalusite, kyanite, and sillimanite, containing both Fe2+-Fe3+ and Fe2+-Ti4+ intervalence charge transfer (IVCT) absorption bands were measured at temperatures up to 1000 °C. Upon heating, thermally equilibrated IVCT bands significantly decreased in intensity and recovered fully on cooling. These trends contrast with the behavior of crystal field bands at temperature for Fe, Cr, and V in corundum, kyanite, and spinel. The effects of cation diffusion and aggregation, as well as the redistribution of band intensity at temperature, are also discussed. The loss of absorption intensity in the visible and near-infrared regions of the spectrum of these phases may point to a more general behavior of IVCT in minerals at temperatures within the Earth with implications for radiative conductivity within the Earth. 

Optical photothermal infrared spectroscopy (O-PTIR) was used to characterize a terrestrial rock sample as a demonstration of the technique’s enhanced spatial resolution as it corresponds to minerology and the detection of organics. Traditional reflectance-based infrared techniques are limited by the wavelength of the infrared light interacting with the surface along with additional optical dispersion issues. However, because of the nature in which the infrared spectrum is measured via O-PTIR, these traditional issues are eliminated. This is possible through the recent developments of high intensity quantum cascade-based infrared lasers capable of scanning the mid infrared spectrum (3000–500 cm−1). Individual O-PTIR and diffuse reflectance data were collected on a terrestrial rock sample and compared to a recent discovery of NASA JPL’s Perseverance Rover regarding inclusions of comparable size. In addition, an O-PTIR map of a particularly dense area of proteinaceous material in the terrestrial sample was collected, further exemplifying the capability. This technique has significant potential for use regarding future returned Mars samples and in situ planetary surface science when considering the spatial resolution, sensitivity, and negligible sample preparation.