Role of acentric displacements on the crystal structure and second-harmonic generating properties of RbPbCO3F and CsPbCO3F

T. Thao Tran, P. Shiv Halasyamani*, James M. Rondinelli

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

63 Scopus citations


Two lead fluorocarbonates, RbPbCO3F and CsPbCO3F, were synthesized and characterized. The materials were synthesized through solvothermal and conventional solid-state techniques. RbPbCO3F and CsPbCO3F were structurally characterized by single-crystal X-ray diffraction and exhibit three-dimensional (3D) crystal structures consisting of corner-shared PbO6F2 polyhedra. For RbPbCO3F, infrared and ultraviolet-visible spectroscopy and thermogravimetric and differential thermal analysis measurements were performed. RbPbCO3F is a new noncentrosymmetric material and crystallizes in the achiral and nonpolar space group P6̄m2 (crystal class 6̄m2). Powder second-harmonic generation (SHG) measurements on RbPbCO3F and CsPbCO3F using 1064 nm radiation revealed an SHG efficiency of approximately 250 and 300 × α-SiO2, respectively. Charge constants d33 of approximately 72 and 94 pm/V were obtained for RbPbCO3F and CsPbCO3F, respectively, through converse piezoelectric measurements. Electronic structure calculations indicate that the nonlinear optical response originates from the distorted PbO6F 2 polyhedra, because of the even-odd parity mixing of the O 2p states with the nearly spherically symmetric 6s electrons of Pb2+. The degree of inversion symmetry breaking is quantified using a mode-polarization vector analysis and is correlated with cation size mismatch, from which it is possible to deduce the acentric properties of 3D alkali-metal fluorocarbonates.

Original languageEnglish (US)
Pages (from-to)6241-6251
Number of pages11
JournalInorganic chemistry
Issue number12
StatePublished - Jun 16 2014

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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