Bent HgI2 Molecules in the Melt and Sulfide Glasses: Implications for Nonlinear Optics

Kassem, Mohammad; Bokova, Maria; Tverjanovich, Andrey S.; Fontanari, Daniele; Le Coq, David; Sokolov, Anton; Masselin, Pascal; Kohara, Shinji; Usuki, Takeshi; Hannon, Alex C.; Benmore, Chris J.; Bychkov, Eugene

doi:10.1021/acs.chemmater.9b00860

Bent HgI₂ Molecules in the Melt and Sulfide Glasses: Implications for Nonlinear Optics

Journal Article · Thu May 09 00:00:00 EDT 2019 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.9b00860· OSTI ID:1572410

^[1]; Bokova, Maria ^[1]; Tverjanovich, Andrey S. ^[2]; Fontanari, Daniele ^[1]; Le Coq, David ^[3]; Sokolov, Anton ^[1]; Masselin, Pascal ^[1]; Kohara, Shinji ^[4]; Usuki, Takeshi ^[5]; ^[6]; Benmore, Chris J. ^[7]; ^[1]

Univ. of the Littoral Opal Coast (ULCO), Dunkerque (France)
St. Petersburg State Univ. (Russia)
Univ. of Rennes (France)
National Inst. for Materials Science (NIMS), Tsukuba (Japan)
Yamagata Univ. (Japan)
Rutherford Appleton Lab. (United Kingdom)
Argonne National Lab. (ANL), Argonne, IL (United States)

Nonlinear optical (NLO) crystals are widely used in advanced photonic technologies for second harmonic and difference frequency generation (SHG and DFG, respectively), producing coherent light at frequencies where existing lasers are unavailable. Isotropic glasses do not exhibit SHG or DFG, except temporarily induced anisotropy under external stimuli. Nevertheless, recent reports on glasses with chiral structural motifs show promising permanent NLO properties. We introduce an alternative solution: hybrid molecular/network glasses with noncentrosymmetric HgI₂ monomers. Mercury (II) iodide consists of linear HgI₂ triatomic molecules in the vapor phase and in the yellow orthorhombic polymorph stable above 400 K. At lower temperatures, the tetragonal red form is composed of corner-sharing HgI_4/2 tetrahedra forming a layered extended framework. There is a gap in the molecular evolution; direct structural measurements of the liquid HgI₂ phase are missing. Using high-energy X-ray scattering, pulsed neutron diffraction, and Raman spectroscopy supported by structural and vibrational modeling, we show that the mercury(II) iodide melt and HgI₂-containing sulfide glasses are built up by bent HgI₂ monomers (the bond angle

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: Agence Nationale de la recherche (ANR); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1572410

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 11 Vol. 31; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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