Microscopic origins of optical second harmonic generation in noncentrosymmetric-nonpolar materials

Antonio Cammarata*, Weiguo Zhang, P. Shiv Halasyamani, James M. Rondinelli

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

72 Scopus citations


We use a symmetry-based structural analysis combined with an electronic descriptor for bond covalency to explain the origin of the second-order nonlinear optical response (second harmonic generation, SHG) in noncentrosymmetric nonpolar ATeMoO6 compounds (where A = Mg, Zn, or Cd). We show that the SHG response has a complex dependence on the asymmetric geometry of the AO6 and AO4 functional units and the orbital character at the valence band edge, which we are able to distinguish using an A-O bond covalency descriptor. The degree of covalency between the divalent A-site cation and the oxygen ligands dominates over the geometric contributions to the SHG arising from the acentric polyhedra, and this can be understood from considerations of the local static charge density distribution. The use of a local dipole model for the polyhedral moieties (AO4/AO6, MoO4, and TeO4) can account for a nonzero SHG response, even though the materials exhibit nonpolar structures; however, it is insufficient to explain the change in the magnitude of the SHG response upon A-cation substitution. The atomic scale and electronic structure understanding of the macroscopic SHG behavior is then used to identify hypothetical HgTeMoO6 as a candidate telluromolybdate with an enhanced nonlinear optical response. (Figure Presented).

Original languageEnglish (US)
Pages (from-to)5773-5781
Number of pages9
JournalChemistry of Materials
Issue number19
StatePublished - Oct 14 2014

ASJC Scopus subject areas

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


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