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We present a method to determine the bulk temperature of a single crystal diamond sample at an X-Ray free electron laser using inelastic X-ray scattering. The experiment was performed at the high energy density instrument at the European XFEL GmbH, Germany. The technique, based on inelastic X-ray scattering and the principle of detailed balance, was demonstrated to give accurate temperature measurements, within 8% for both room temperature diamond and heated diamond to 500 K. Here, the temperature was increased in a controlled way using a resistive heater to test theoretical predictions of the scaling of the signal with temperature. The method was tested by validating the energy of the phonon modes with previous measurements made at room temperature using inelastic X-ray scattering and neutron scattering techniques. This technique could be used to determine the bulk temperature in transient systems with a temporal resolution of 50 fs and for which accurate measurements of thermodynamic properties are vital to build accurate equation of state and transport models.From the thermal shield of a spacecraft during atmospheric re-entry 1 to the interior of Jovian planets 2 , matter is often found at pressures and temperatures that are at the limits of where conventional condensed matter and plasma physics formalisms are valid 3 . At such extreme conditions, the kinetic energy of the electrons is comparable to the potential energy of interaction between electrons and the nuclei. For these systems, direct and accurate measurements of thermodynamic and transport properties are vital. Extreme states of matter can be produced by dynamic laser-driven compression [4][5][6] and laser heating techniques 7,8 . These methods can excite a material into a transient state of simultaneously high density and temperature, and thereby enable access to previously unexplored regions of phase space. State-of-the-art experiments investigate the properties of materials driven into these conditions by coupling high-energy lasers with suitable probing techniques 9,10 . In particular, X-ray scattering has proven to be a powerful tool for determining the structure and density, and the development of

The properties of all materials at one atmosphere of pressure are controlled by the configurations of their valence electrons. At extreme pressures, neighboring atoms approach so close that core-electron orbitals overlap, and theory predicts the emergence of unusual quantum behavior. We ramp-compress monovalent elemental sodium, a prototypical metal at ambient conditions, to nearly 500 GPa (5 million atmospheres). The 7-fold increase of density brings the interatomic distance to 1.74 Å well within the initial 2.03 Å of the Na+ ionic diameter, and squeezes the valence electrons into the interstitial voids suggesting the formation of an electride phase. The laser-driven compression results in pressure-driven melting and recrystallization in a billionth of a second. In situ x-ray diffraction reveals a series of unexpected phase transitions upon recrystallization, and optical reflectivity measurements show a precipitous decrease throughout the liquid and solid phases, where the liquid is predicted to have electronic localization. These data reveal the presence of a rich, temperature-driven polymorphism where core electron overlap is thought to stabilize the formation of peculiar electride states.

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