Effect of Pressure on the Distribution of Electrons in a Cluster of H₂S

We carry out a theoretical study of the effect of pressure on the atomic and electronic distribution of a cluster made of 155 H₂S molecules. The pressure was modeled by bringing the cluster into a spherical container made of 500 helium atoms and reducing the diameter of the container. We did ab initio molecular calculations using DFT. At the lowest pressure, the S-H-S angle between two neighboring H₂S molecules has a distribution with a mean value of 167.1°. This angle will be shorter as pressure increases, reaching a distribution with a mean value of 125.5° at the highest pressure. Changes in this angle result from a strong S-S interaction, displacing the H atoms from the line joining the sulfur atoms. This rearrangement of the atomic distribution generates hydrogen-rich spatial regions. We analyzed the evolution of Mulliken charges on S and H atoms in the cluster with pressure, finding that electrons move from S to H atoms, suggesting that these hydrogen-rich regions should be responsible for the electrical conductivity and, consequently, also for the superconductivity in solid H₂S under pressure.