title: Metallization of a hypervalent radical dimer: molecular and band perspectives.
abstract: Variable pressure and temperature conductivity measurements on the bisthiaselenazolyl radical dimer [1a](2) have established the presence of a weakly metallic state over the pressure range 5-9 GPa. To explore the origin of this metallization we have examined the crystal and molecular structure of [1a](2) as a function of pressure. At ambient pressure the dimer consists of two radicals linked by a hypervalent 4-center 6-electron S...Se-Se...S sigma-bond into an essentially coplanar arrangement. The dimers are packed in cross-braced slipped pi-stack arrays running along the x-direction of the monoclinic (space group P2(1)/c) unit cell. Pressurization to 4 GPa induces little change in the molecular structure of [1a](2) or in the slipped pi-stack crystal architecture. Near 5 GPa, however, stress on the dimer leads to buckling of the two halves of the molecule and a contraction in the metrics of the S...Se-Se...S unit. These structural changes can be understood in terms of an electronic configurational switch from a 4-center 6-electron sigma-bonded dimer to a more conventional pi-bonded arrangement. At the same time the slipped pi-stack arrays undergo a concertina-like compression, and the crystal structure experiences highly anisotropic changes in cell dimensions. DFT calculations on the molecular electronic structure of the dimer indicate a marked decrease in the HOMO-LUMO gap as the dimer buckles. Related solid-state calculations indicate a rapid closure of the valence/conduction band gap in the same pressure region and the formation of a quasi-metallic state. Metallization of [1a](2) thus arises as much from intramolecular changes, which give rise to a collapse of the HOMO-LUMO gap and near coalescence of the valence and conduction bands, as from increased intermolecular interactions, which cause widening and overlap of the band edges.
authors.affiliation: Department of Physics and Engineering Physics, University of Saskatchewan, Saskatoon, Saskatchewan S7N 5E2, Canada.
authors.forename: John S
authors.initials: JS
authors.lastname: Tse
authors.forename: Alicea A
authors.initials: AA
authors.lastname: Leitch
authors.forename: Xueyang
authors.initials: X
authors.lastname: Yu
authors.forename: Xuezhao
authors.initials: X
authors.lastname: Bao
authors.forename: Sijia
authors.initials: S
authors.lastname: Zhang
authors.forename: Qingqing
authors.initials: Q
authors.lastname: Liu
authors.forename: Changqing
authors.initials: C
authors.lastname: Jin
authors.forename: Richard A
authors.initials: RA
authors.lastname: Secco
authors.forename: Serge
authors.initials: S
authors.lastname: Desgreniers
authors.forename: Yasuo
authors.initials: Y
authors.lastname: Ohishi
authors.forename: Richard T
authors.initials: RT
authors.lastname: Oakley
mesh_terms: D003198:Computer Simulation; D019281:Dimerization; D004553:Electric Conductivity; D005609:Free Radicals / Q000737:chemistry; D008956:Models, Chemical; D009942:Organometallic Compounds / Q000737:chemistry*; D011312:Pressure; D012643:Selenium / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry; D013696:Temperature
chemical_list: D005609:Free Radicals; D009942:Organometallic Compounds; D013438:Sulfhydryl Compounds; D012643:Selenium