Probing iron spin state by optical absorption in laser-heated diamond anvil cell

Abstract:

Pressure-induced spin-pairing transitions in iron-bearing minerals have been in the focus of geophysical studies¹. Modern consensus is that iron spin state in the lower mantle is a complex function of crystal structure, composition, pressure, and temperature. Discontinuities in physical properties of lower mantle minerals have been revealed over the spin transition pressure range, but at room temperature. In this work, we have used a supercontinuum laser source and an intensified CCD camera to probe optical properties of siderite, FeCO₃, and post-perovskite, Mg_0.9Fe_0.1SiO₃, across the spin transition in laser-heated diamond anvil cell. Synchronously gating the CCD with the supercontinuum pulses (Fig. 1A) allowed diminishing thermal background to ~8.3*10^-4. Utilizing the experimental setup we infer the spin state of ferrous iron in siderite at high pressure and temperature conditions (Fig. 1B). Similar behavior is observed for low spin ferric iron in post-perovskite at 130 GPa indicating that all iron in post-perovskite is high spin at lower mantle conditions. Also, our experimental setup holds promise for measuring radiative thermal conductivity of mantle minerals at relevant mantle conditions.

Figure 1. (A) Timing of the optical absorption measurements at high temperature. (B) High temperature siderite absorption spectra at 45 GPa. Before heating and quenched after 1300 K spectra are shown in light and dark blue, respectively. Green and red curves are absorption spectra at 1200 K and 1300 K, respectively. Spectra shown in black represent room temperature absorption data on HS (43 GPa) and LS (45.5 GPa) siderite after Lobanov et al., 2015, shown for comparison.