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

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

Research outputpeer-review

Abstract

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. However, recent reports on glasses with chiral structural motifs show promising permanent NLO properties. We propose 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 HgI4/2 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 <I-Hg-I = 156 ± 2° in the melt). The noncentrosymmetric entities imply intrinsic optical nonlinearity of the second order, confirmed by a strong SHG response.

Original languageEnglish
Pages (from-to)4103-4112
Number of pages10
JournalChemistry of Materials
Volume31
Issue number11
DOIs
Publication statusPublished - 11 Jun 2019

Fingerprint

Nonlinear optics
Sulfides
Glass
Molecules
Iodides
Mercury
Monomers
Neutron diffraction
Polymorphism
X ray scattering
Photonics
Raman spectroscopy
Anisotropy
Optical properties
Vapors
Crystals
red mercuric iodide
Lasers
Liquids
Temperature

Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Cite this

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. / Bent HgI2 Molecules in the Melt and Sulfide Glasses: Implications for Nonlinear Optics. In: Chemistry of Materials. 2019 ; Vol. 31, No. 11. pp. 4103-4112.
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abstract = "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. However, recent reports on glasses with chiral structural motifs show promising permanent NLO properties. We propose 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 HgI4/2 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 <I-Hg-I = 156 ± 2° in the melt). The noncentrosymmetric entities imply intrinsic optical nonlinearity of the second order, confirmed by a strong SHG response.",
author = "Mohammad Kassem and Maria Bokova and Tverjanovich, {Andrey S.} and Daniele Fontanari and {Le Coq}, David and Anton Sokolov and Pascal Masselin and Shinji Kohara and Takeshi Usuki and Hannon, {Alex C.} and Benmore, {Chris J.} and Eugene Bychkov",
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Kassem, M, Bokova, M, Tverjanovich, AS, Fontanari, D, Le Coq, D, Sokolov, A, Masselin, P, Kohara, S, Usuki, T, Hannon, AC, Benmore, CJ & Bychkov, E 2019, 'Bent HgI2 Molecules in the Melt and Sulfide Glasses: Implications for Nonlinear Optics', Chemistry of Materials, vol. 31, no. 11, pp. 4103-4112. https://doi.org/10.1021/acs.chemmater.9b00860

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.

In: Chemistry of Materials, Vol. 31, No. 11, 11.06.2019, p. 4103-4112.

Research outputpeer-review

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AU - Kassem, Mohammad

AU - Bokova, Maria

AU - Tverjanovich, Andrey S.

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AU - Le Coq, David

AU - Sokolov, Anton

AU - Masselin, Pascal

AU - Kohara, Shinji

AU - Usuki, Takeshi

AU - Hannon, Alex C.

AU - Benmore, Chris J.

AU - Bychkov, Eugene

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N2 - 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. However, recent reports on glasses with chiral structural motifs show promising permanent NLO properties. We propose 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 HgI4/2 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 <I-Hg-I = 156 ± 2° in the melt). The noncentrosymmetric entities imply intrinsic optical nonlinearity of the second order, confirmed by a strong SHG response.

AB - 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. However, recent reports on glasses with chiral structural motifs show promising permanent NLO properties. We propose 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 HgI4/2 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 <I-Hg-I = 156 ± 2° in the melt). The noncentrosymmetric entities imply intrinsic optical nonlinearity of the second order, confirmed by a strong SHG response.

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