Density functional theory (DFT) studies of hydrogen rich solids and boron carbide under extreme conditions

Abstract

Since the first prediction that compressed hydrogen would metallize in 1935 and the further prediction that the metallic allotrope would be a superconductor at high temperatures, metallic hydrogen has been termed the “holy grail” of high-pressure science. A tremendous amount of theoretical and experimental research has been carried out, with the ultimate goal of metallizing hydrogen via the application of external pressure. It has been previously proposed that doping hydrogen with another element can lower the pressure at which metallization occurs. A number of experimental and theoretical studies have investigated doping hydrogen by either a group XIII or XIV element. Experiments in diamond anvil cells have illustrated that it is indeed possible to synthesize hydrogen-rich phases under conditions of extreme pressures, and SiH 4 (H 2 ) 2 , GeH 4 (H 2 ) n , and Xe(H 2 ) n have been shown to behave as true compounds. The focus herein is on the theoretical exploration of hydrogen-rich phases with novel stoichiometries, which contain a dopant element up to pressures of 350 GPa. In particular, the alkali-metal and alkaline Earth metal polyhydrides (MH n where n > 1) have been considered. Within this thesis the XtalOpt evolutionary algorithm was employed in order to complete this work, and predict the most stable structures of cesium and beryllium polyhydrides under pressure. In addition, we explore the possibility of mixing excess hydrogen with an electronegative element, iodine and phosphorus. The phases found are examined via detailed first principles calculations. In addition, because of its outstanding hardness, thermodynamic stability, low density, electronic properties, thermal stability, and high melting point boron carbide has many uses: i.e. as a refractory material, in abrasive powders and ballistics, as a neutron radiation absorbent, and in electronic applications. However, little is known about the behavior of boron carbide when under the external stress of pressure. The shock compression of boron carbide has been widely studied for decades both experimentally and theoretically. Due to its low density and high shock strength boron carbide is a candidate for use in ballistic applications, such as armor. However, even with the 40 years of boron carbide shocks, its properties and response while in a shocked state have remained difficult to ascertain. A series of first-principles equation of state (EOS) calculations of B4 C that are in excellent agreement with existing Omega laser measurements have been conducted. Furthermore, in the P-T range to 1.5 TPa and 60,000 K the EOS has been extended. These results are relevant for ongoing and future experimental efforts at high-energy laser facilities such as the National Ignition Facility at Lawrence Livermore National Laboratory.