title: Novel cooperative interactions and structural ordering in H2S-H2.
abstract: Hydrogen sulfide (H(2)S) and hydrogen (H(2)) crystallize into a 'guest-host' structure at 3.5 GPa and, at the initial formation pressure, the rotationally disordered component molecules exhibit weak van der Waals-type interactions. With increasing pressure, hydrogen bonding develops and strengthens between neighboring H(2)S molecules, reflected in a pronounced drop in S-H vibrational stretching frequency and also observed in first-principles calculations. At 17 GPa, an ordering process occurs where H(2)S molecules orient themselves to maximize hydrogen bonding and H(2) molecules simultaneously occupy a chemically distinct lattice site. Intermolecular forces in the H(2)S+H(2) system may be tuned with pressure from the weak hydrogen-bonding limit to the ordered hydrogen-bonding regime, resulting in a novel clathrate structure stabilized by cooperative interactions.
authors.affiliation: Geophysical Laboratory, Carnegie Institution of Washington, Washington, DC 20015, USA. tstrobel@ciw.edu
authors.forename: Timothy A
authors.initials: TA
authors.lastname: Strobel
authors.forename: P
authors.initials: P
authors.lastname: Ganesh
authors.forename: Maddury
authors.initials: M
authors.lastname: Somayazulu
authors.forename: P R C
authors.initials: PR
authors.lastname: Kent
authors.forename: Russell J
authors.initials: RJ
authors.lastname: Hemley