First-principles study lone-pair effects of Sb (III)-S chromophore influence on SHG response in quaternary potassium containing silver antimony sulfides
| Autor: | Junben Huang, Bing-Hua Lei, Xin Su, Dianwei Hou, Zhihua Yang, Shilie Pan |
|---|---|
| Rok vydání: | 2017 |
| Předmět: |
Stereochemistry
Potassium chemistry.chemical_element Second-harmonic generation 02 engineering and technology Electronic structure Chromophore 010402 general chemistry 021001 nanoscience & nanotechnology Condensed Matter Physics 01 natural sciences 0104 chemical sciences Electronic Optical and Magnetic Materials Inorganic Chemistry Crystallography Nonlinear optical Antimony chemistry Materials Chemistry Ceramics and Composites Density functional theory Physical and Theoretical Chemistry 0210 nano-technology Lone pair |
| Zdroj: | Journal of Solid State Chemistry. 249:215-220 |
| ISSN: | 0022-4596 |
| DOI: | 10.1016/j.jssc.2017.03.003 |
| Popis: | First-principles studies of the geometric structures, electronic structures and optical properties of non-centrosymmetrical (NCS) KAg 2 SbS 4 , K 2 AgSbS 4 and K 2 Ag 3 Sb 3 S 7 and centrosymmetrical (CS) KAg 2 SbS 3 and K 3 Ag 9 Sb 4 S 12 have been performed by means of density functional theory. It is indicated that although they have similarity in their anionic groups and, the electronic structures, prominent features of the optical anisotropy or second-order nonlinear optical (NLO) susceptibilities are apparently different. The calculated birefringences are 0.0537, 0.0343, 0.1324, 0.2217 and 0.0604 which are attributed to the different anionic groups [SbS 3 ] and triangles [AgS 3 ]. Also, the calculated NLO responses are about 0.5×, 1.0× and 2.0× times than that commercial AgGaS 2 (AGS, d 36 =11 pm/V) for K 2 AgSbS 4 , KAg 2 SbS 4 and K 2 Ag 3 Sb 3 S 7 , respectively. In comparison with the absolute magnitude of second harmonic generation (SHG) coefficients, the order K 2 Ag 3 Sb 3 S 7 >KAg 2 SbS 4 >K 2 AgSbS 4 is clearly established in the SHG response. Further analysis based on the real-space atom-cutting method reveals that the main sources of the SHG properties of these compounds are from the Sb-S group, especially K 2 Ag 3 Sb 3 S 7 is mainly attributed to the lone pair stereochemical activity of Sb (III)-S group. |
| Databáze: | OpenAIRE |
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