Journal article
Role of Acentric Displacements on the Crystal Structure and Second-Harmonic Generating Properties of RbPbCO3F and CsPbCO3F
Inorganic chemistry, v 53(12), pp 6241-6251
16 Jun 2014
PMID: 24867361
Abstract
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 0 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 P (6) over bar m2 (crystal class (6) over bar m2). Powder second-harmonic generation (SHG) measurements on RbPbCO3F and CsPbCO3F using 1064 nm radiation revealed an SHG efficiency of approximately 250 and 300 x alpha-SiO2, respectively. Charge constants d(33) 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 PbO6F2 polyhedra, because of the even-odd parity mixing of the 0 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.
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Details
- Title
- Role of Acentric Displacements on the Crystal Structure and Second-Harmonic Generating Properties of RbPbCO3F and CsPbCO3F
- Creators
- T. Thao Tran - University of HoustonP. Shiv Halasyamani - University of HoustonJames M. Rondinelli - Drexel University
- Publication Details
- Inorganic chemistry, v 53(12), pp 6241-6251
- Publisher
- American Chemical Society; Washington, DC
- Number of pages
- 11
- Grant note
- State of IllinoisU Robert H. Lurie Comprehensive Cancer center E-1457 / Welch Foundation; The Welch Foundation Keck Foundation; W.M. Keck Foundation W. M. Keck Foundation; W.M. Keck Foundation Rice Foundation NSF-NSEC; National Science Foundation (NSF) 52138-DNI10 / American Chemical Society Petroleum Research Fund; American Chemical Society National Institutes of Health; United States Department of Health & Human Services; National Institutes of Health (NIH) - USA Ludo Frevel Crystallography Scholarship DE-SC0005032 / United States Department of Energy Basic Energy Sciences; United States Department of Energy (DOE) NSF-MRSEC; National Science Foundation (NSF); NSF - Directorate for Mathematical & Physical Sciences (MPS)
- Resource Type
- Journal article
- Language
- English
- Web of Science ID
- WOS:000337557800045
- Scopus ID
- 2-s2.0-84902521772
- Other Identifier
- 991019330796704721
InCites Highlights
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- Collaboration types
- Domestic collaboration
- Web of Science research areas
- Chemistry, Inorganic & Nuclear