Helium is the smallest and the lightest noble gas and one of the most unreactive elements, so it was commonly considered that helium compounds cannot exist at all, or at least under normal conditions. Helium's first ionization energy of 24.57 eV is the highest of any element. Helium has a complete shell of electrons, and in this form the atom does not readily accept any extra electrons nor join with anything to make covalent compounds. The electron affinity is 0.080 eV, which is very close to zero. The helium atom is small with the radius of the outer electron shell at 0.29 Å. Helium is a very hard atom with a Pearson hardness of 12.3 eV. It has the lowest polarizability of any kind of atom, however, very weak van der Waals forces exist between helium and other atoms. This force may exceed repulsive forces, so at extremely low temperatures helium may form van der Waals molecules. Helium has the lowest boiling point (4.2 K) of any known substance.
Repulsive forces between helium and other atoms may be overcome by high pressures. Helium has been shown to form a crystalline compound with sodium under pressure. Suitable pressures to force helium into solid combinations could be found inside planets. Clathrates are also possible with helium under pressure in ice, and other small molecules such as nitrogen.
Other ways to make helium reactive are: to convert it into an ion, or to excite an electron to a higher level, allowing it to form excimers. Ionised helium (He+), also known as He II, is a very high energy material able to extract an electron from any other atom. He+ has an electron configuration like hydrogen, so as well as being ionic it can form covalent bonds. Excimers do not last for long, as the molecule containing the higher energy level helium atom can rapidly decay back to a repulsive ground state, where the two atoms making up the bond repel. However, in some locations such as helium white dwarfs, conditions may be suitable to rapidly form excited helium atoms. The excited helium atom has a 1s electron promoted to 2s. This requires per gram of helium, which can be supplied by electron impact, or electric discharge. The 2s excited electron state resembles that of the lithium atom.
Known solid phases
Most solid combinations of helium with other substances require high pressure. Helium does not bond with the other atoms, but the substances can have a well defined crystal structure.
Disodium helide
Disodium helide (Na2He) is a compound of helium and sodium that is stable at high pressures above . Disodium helide was first predicted using USPEX code and was first synthesised in 2016. It was predicted to be thermodynamically stable over 160 GPa and dynamically stable over 100 GPa. Na2He has a cubic crystal structure, resembling fluorite. At 300 GPa the edge of a unit cell of the crystal has . Each unit cell contains four helium atoms on the centre of the cube faces and corners, and eight sodium atoms at coordinates a quarter cell in from each face. Double electrons (2e−) are positioned on each edge and the centre of the unit cell. Each pair of electrons is spin paired. The presence of these isolated electrons makes this an electride. The helium atoms do not participate in any bonding. However the electron pairs can be considered as an eight-centre two-electron bond. Disodium helide is predicted to be an insulator and transparent.
Silicates
Helium was first observed to enter into a silicate in 2007. The mineral melanophlogite is a natural silica clathrate (clathrasil) that normally would contain carbon dioxide, methane or nitrogen. When compressed with helium, a new clathrate forms. This has a much higher bulk modulus, and resists amorphization. Helium was taken up around 17 GPa, enlarging the unit cell, and given off again when pressure dropped to 11 GPa.
Cristobalite He II (SiO2He) is stable between 1.7 and 6.4 GPa. It has a rhombohedral space group R-3c with unit cell dimensions and at 4 GPa.
Cristobalite He I (SiO2He) can be formed under higher helium pressures over 6.4 GPa. It has a monoclinic space group P21/C with unit cell dimensions and at 10 GPa.
Helium penetrates into fused silica at high pressure, reducing its compressibility.
Chibaite, another natural silica clathrate has its structure penetrated by helium under pressures higher than 2.5 GPa. The presence of guest hydrocarbons does not prevent this happening. Neon requires a higher pressure, 4.5 GPa to penetrate, and unlike helium shows hysteresis. Linde-type A zeolites are also rendered less compressible when penetrated by helium between 2 and 7 GPa.