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Title: First-principles study lone-pair effects of Sb (III)-S chromophore influence on SHG response in quaternary potassium containing silver antimony sulfides

Abstract

First-principles studies of the geometric structures, electronic structures and optical properties of non-centrosymmetrical (NCS) KAg{sub 2}SbS{sub 4}, K{sub 2}AgSbS{sub 4} and K{sub 2}Ag{sub 3}Sb{sub 3}S{sub 7} and centrosymmetrical (CS) KAg{sub 2}SbS{sub 3} and K{sub 3}Ag{sub 9}Sb{sub 4}S{sub 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{sub 3}] and triangles [AgS{sub 3}]. Also, the calculated NLO responses are about 0.5×, 1.0× and 2.0× times than that commercial AgGaS{sub 2} (AGS, d{sub 36}=11 pm/V) for K{sub 2}AgSbS{sub 4}, KAg{sub 2}SbS{sub 4} and K{sub 2}Ag{sub 3}Sb{sub 3}S{sub 7}, respectively. In comparison with the absolute magnitude of second harmonic generation (SHG) coefficients, the order K{sub 2}Ag{sub 3}Sb{sub 3}S{sub 7}>KAg{sub 2}SbS{sub 4}>K{sub 2}AgSbS{sub 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{sub 2}Ag{sub 3}Sb{sub 3}S{sub 7} is mainlymore » attributed to the lone pair stereochemical activity of Sb (III)-S group. - Graphical abstract: Compounds K{sub 2}AgSbS{sub 4}, KAg{sub 2}SbS{sub 4} and K{sub 2}Ag{sub 3}Sb{sub 3}S{sub 7} exhibit second-order NLO response: 15×, 30× and 62× times than that KDP (KH{sub 2}PO{sub 4}, d{sub 36}=0.39 pm/V), respectively. First-principles methods reveal that the large SHG response of K{sub 2}Ag{sub 3}Sb{sub 3}S{sub 7} is dominated by the Sb-S chromophore with lone pairs.« less

Authors:
 [1];  [2]; ; ;  [1];  [2];  [1];  [1]
  1. Key Laboratory of Functional Materials and Devices for Special Environments of CAS,, Xinjiang Key Laboratory of Electronic Information Materials and Devices, Xinjiang Technical Institute of Physics & Chemistry of CAS, 40-1 South Beijing Road, Urumqi 830011 (China)
  2. (China)
Publication Date:
OSTI Identifier:
22658280
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 249; Other Information: Copyright (c) 2017 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANTIMONY SULFIDES; DENSITY FUNCTIONAL METHOD; ELECTRONIC STRUCTURE; HARMONIC GENERATION; OPTICAL PROPERTIES; POTASSIUM PHOSPHATES; SILVER COMPOUNDS

Citation Formats

Huang, Junben, School of Physics Science and Technology, Xinjiang University, Urumqi 830046, Su, Xin, Hou, Dianwei, Lei, Binghua, University of Chinese Academy of Sciences, Beijing 100049, Yang, Zhihua, E-mail: zhyang@ms.xjb.ac.cn, and Pan, Shilie, E-mail: slpan@ms.xjb.ac.cn. First-principles study lone-pair effects of Sb (III)-S chromophore influence on SHG response in quaternary potassium containing silver antimony sulfides. United States: N. p., 2017. Web. doi:10.1016/J.JSSC.2017.03.003.
Huang, Junben, School of Physics Science and Technology, Xinjiang University, Urumqi 830046, Su, Xin, Hou, Dianwei, Lei, Binghua, University of Chinese Academy of Sciences, Beijing 100049, Yang, Zhihua, E-mail: zhyang@ms.xjb.ac.cn, & Pan, Shilie, E-mail: slpan@ms.xjb.ac.cn. First-principles study lone-pair effects of Sb (III)-S chromophore influence on SHG response in quaternary potassium containing silver antimony sulfides. United States. doi:10.1016/J.JSSC.2017.03.003.
Huang, Junben, School of Physics Science and Technology, Xinjiang University, Urumqi 830046, Su, Xin, Hou, Dianwei, Lei, Binghua, University of Chinese Academy of Sciences, Beijing 100049, Yang, Zhihua, E-mail: zhyang@ms.xjb.ac.cn, and Pan, Shilie, E-mail: slpan@ms.xjb.ac.cn. Mon . "First-principles study lone-pair effects of Sb (III)-S chromophore influence on SHG response in quaternary potassium containing silver antimony sulfides". United States. doi:10.1016/J.JSSC.2017.03.003.
@article{osti_22658280,
title = {First-principles study lone-pair effects of Sb (III)-S chromophore influence on SHG response in quaternary potassium containing silver antimony sulfides},
author = {Huang, Junben and School of Physics Science and Technology, Xinjiang University, Urumqi 830046 and Su, Xin and Hou, Dianwei and Lei, Binghua and University of Chinese Academy of Sciences, Beijing 100049 and Yang, Zhihua, E-mail: zhyang@ms.xjb.ac.cn and Pan, Shilie, E-mail: slpan@ms.xjb.ac.cn},
abstractNote = {First-principles studies of the geometric structures, electronic structures and optical properties of non-centrosymmetrical (NCS) KAg{sub 2}SbS{sub 4}, K{sub 2}AgSbS{sub 4} and K{sub 2}Ag{sub 3}Sb{sub 3}S{sub 7} and centrosymmetrical (CS) KAg{sub 2}SbS{sub 3} and K{sub 3}Ag{sub 9}Sb{sub 4}S{sub 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{sub 3}] and triangles [AgS{sub 3}]. Also, the calculated NLO responses are about 0.5×, 1.0× and 2.0× times than that commercial AgGaS{sub 2} (AGS, d{sub 36}=11 pm/V) for K{sub 2}AgSbS{sub 4}, KAg{sub 2}SbS{sub 4} and K{sub 2}Ag{sub 3}Sb{sub 3}S{sub 7}, respectively. In comparison with the absolute magnitude of second harmonic generation (SHG) coefficients, the order K{sub 2}Ag{sub 3}Sb{sub 3}S{sub 7}>KAg{sub 2}SbS{sub 4}>K{sub 2}AgSbS{sub 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{sub 2}Ag{sub 3}Sb{sub 3}S{sub 7} is mainly attributed to the lone pair stereochemical activity of Sb (III)-S group. - Graphical abstract: Compounds K{sub 2}AgSbS{sub 4}, KAg{sub 2}SbS{sub 4} and K{sub 2}Ag{sub 3}Sb{sub 3}S{sub 7} exhibit second-order NLO response: 15×, 30× and 62× times than that KDP (KH{sub 2}PO{sub 4}, d{sub 36}=0.39 pm/V), respectively. First-principles methods reveal that the large SHG response of K{sub 2}Ag{sub 3}Sb{sub 3}S{sub 7} is dominated by the Sb-S chromophore with lone pairs.},
doi = {10.1016/J.JSSC.2017.03.003},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 249,
place = {United States},
year = {Mon May 15 00:00:00 EDT 2017},
month = {Mon May 15 00:00:00 EDT 2017}
}