Observation of iron spin-states using tabletop x-ray emission spectroscopy and microcalorimeter sensors

X-ray emission spectroscopy (XES) is a powerful probe of the electronic and chemical state of elemental species embedded within complex compounds. X-ray sensors that combine high resolving power and high collecting efficiency are desirable for photon-starved XES experiments such as measurements of dilute, gaseous, and radiation-sensitive samples, time-resolved measurements, and in-laboratory XES. To assess whether arrays of cryogenic microcalorimeters will be useful in photon-starved XES scenarios, we demonstrate that these emerging energydispersive sensors can detect the spin-state of 3d electrons of iron in two different compounds, Fe2O3 and FeS2. The measurements were conducted with a picosecond pulsed laser-driven plasma as the exciting x-ray source. The use of this tabletop source suggests that time-resolved in-laboratory XES will be possible in the future. We also present simulations of Ka and Kb spectra that reveal the spin-state sensitivity of different combinations of sensor resolution and accumulated counts. These simulations predict that our current experimental apparatus can perform time-resolved XES measurements on some samples with a measurement time of a few 10 s of hours per time delay.