Dense, Subnano Phase of Clustered O2

Condensed O2 tends to form clusters, even with a long-range order. In particular, in solid oxygen, strong intermolecular charge transfer at high pressures leads to the formation of (O2)4 tetramers above 10 GPa, in the ε-O2 phase, with weak O2−O2 chemical bonds. Indeed, ε-O2 is entirely made of these tetramers. We conducted experimental investigations on strongly densified O2 in a different environment, that is to say in the form of a subnano phase build up within the 1D microchannels of a purely siliceous, inert zeolite, TON, at pressures of 0.5−20 GPa, by means of diamond anvil cells. Our X-ray diffraction and infrared and Raman spectroscopy results consistently show that oxygen forms clusters in this nanophase, above 10 GPa, similar to ε-O2, except that the clusters are rather of the type of weakly bonded (O2)2 dimers in this case. Also, by analogy with bulk oxygen, we show that the O2 spin within the dimers departs from S = 1 toward lower values, upon increasing pressure. Our findings thereby add to the general view on essential properties of highly dense oxygen.