后过渡金属中的孤对电子及其对光学响应的贡献（英文）

王嘉龙; 张瑞鑫; 崔秀花; 陈兆慧; 井群; 段海明

doi:10.13568/j.cnki.651094.651316.2023.10.10.0003

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后过渡金属中的孤对电子及其对光学响应的贡献（英文）

数理科学 | 更新时间：2026-01-21

- 后过渡金属中的孤对电子及其对光学响应的贡献（英文）
- 后过渡金属中的孤对电子及其对光学响应的贡献（英文）
- 新疆大学学报（自然科学版中英文） 2024年41卷第5期页码：579-590
- 作者机构：
  
  1. 新疆大学物理科学与技术学院新疆固体物理与器件自治区重点实验室
  2. 新疆大学化工学院石油天然气精细化工教育部和自治区重点实验室
- 作者简介：
- 基金信息：
  
  supported by the National Natural Science Foundation of the People's Republic of China “Mechanistic study of the influence of ns~2 cation intrinsic properties and coordination environment on birefringence and frequency doubling effects”(12264047),“The study of the mechanism of the influence of lead-oxygen polyhedra and their coordination environments on the gain of the frequency doubling effect”(11864040);Tianshan Talent Project of Xinjiang Uygur Autonomous Region of China “Design,synthesis and photofunctional study of novel rare earth phosphate materials”(2022TSYCJU0004)
- DOI：10.13568/j.cnki.651094.651316.2023.10.10.0003
  中图分类号： O641;O469
- 纸质出版：2024
- 稿件说明：
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[1]王嘉龙,张瑞鑫,崔秀花,等.后过渡金属中的孤对电子及其对光学响应的贡献（英文）[J].新疆大学学报(自然科学版中英文),2024,41(05):579-590.
[1]王嘉龙,张瑞鑫,崔秀花,等.后过渡金属中的孤对电子及其对光学响应的贡献（英文）[J].新疆大学学报(自然科学版中英文),2024,41(05):579-590. DOI： 10.13568/j.cnki.651094.651316.2023.10.10.0003.

DOI：10.13568/j.cnki.651094.651316.2023.10.10.0003.

摘要

后过渡金属原子周围的立体化学活性孤对电子在决定扭曲晶格结构和光学响应方面起着重要作用．孤对电子的表征方法包括晶体轨道、电子局部化函数和分波态密度．通过基于现代偏振理论的Born有效电荷的方法对双折射进行评估，探究了双折射和二次谐波响应不同的起源，以及自旋轨道耦合对能带结构和光学性质的影响．这有助于深入理解孤对电子及其对光学性质的贡献．

Abstract

The stereochemically active lone pairs around post-transition metal atoms play an important role in determining distorted lattice structure and optical response. The lone pair electrons are characterized by crystal orbitals

electron localization function(ELF) and partial density of states(PDOS). Birefringence is evaluated by means of a Born effective charge approach based on modern polarization theory. The origin of the different responses of birefringence and second-harmonic generation(SHG) is explored

as well as the effect of spin-orbit coupling(SOC) on the band structure and optical properties is explored. The study of this paper can help to deeply understand the lone pairs and their contribution to optical property.

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references

CHEN C T.An ionic grouping theory of the electro-optical and non-linear optical effects of crystals(I):A theoretical calculation of electro-optical and second optical harmonic coefficients of Barium titanate crystals based on a deformed oxygen-octahedra[J].Acta Physica Sinica,1976,25(2):146-161.

CHEN C T.An ionic grouping theory of the electro-optical and non-linear optical effects of crystals(II):A theoretical calculation of the second harmonic optical coefficients of the lithium iodate crystal based on a highly deformed oxygen-octahedra model I[J].Acta Physica Sinica,1977,26(2):124-132.

CHEN C T.An ionic grouping theory of the electro-optical and non-linear optical effects of crystals(III):A theoretical calculation of the electrooptical and optical second harmonic coefficients for LiNbO3,LiTaO3,KNbO3,and BNN crystals based on a defo[J].Acta Physica Sinica,1977,26(6):486-499.

CHEN C T.An ionic grouping theory of the electro-optical and non-linear optical effects of crystals(IV):The calculation of linear optical susceptibilities in crystals of the perovskite and the tungsten bronze structure types[J].Acta Physica Sinica,1978,27(1):41-46.

CHEN C T,LI T R,WU Y,et al.Nonlinear optical borate crystals:Principals and applications[J].Discrete Mathematics,2012,26(2):43-50.

WANG W K,MEI D J,LIANG F,et al.Inherent laws between tetrahedral arrangement pattern and optical performance in tetrahedron-based mid-infrared nonlinear optical materials[J].Coordination Chemistry Reviews,2020,421:213444.

LIU X M,GONG P F,YANG Y,et al.Nitrate nonlinear optical crystals:A survey on structure-performance relationships[J].Coordination Chemistry Reviews,2019,400:213045.

MUTAILIPU M,POEPPELMEIER K R,PAN S L.Borates:A rich source for optical materials[J].Chemical Reviews,2021,121(3):1130-1202.

MUTAILIPU M,PAN S L.Emergent deep-ultraviolet nonlinear optical candidates[J].Angewandte Chemie International Edition,2020,59(46):20302-20317.

GAO L,HUANG J B,GUO S R,et al.Structure-property survey and computer-assisted screening of mid-infrared nonlinear optical chalcohalides[J].Coordination Chemistry Reviews,2020,421:213379.

CHEN C T,WU B C,JIANG A D,et al.A new-type ultraviolet SHG crystal:β-BaB2O4[J].Scientia Sinica(Series B),1985,28(3):235-243.

CHEN C T,WU Y C,JIANG A D,et al.New nonlinear-optical crystal:LiB3O5[J].Journal of the Optical Society of America B,1989,6(4):616-621.

WU Y C,SASAKI T,NAKAI S D,et al.CsB3O5:A new nonlinear optical crystal[J].Applied Physics Letters,1993,62(21):2614-2615.

MEI L,HUANG X,WANG Y Q,et al.Crystal structure of KBe2BO3F2[J].Zeitschrift F¨ur Kristallographie-Crystalline Materials,1995,210(2):93-95.

CHEN C T,XU Z Y,DENG D Q,et al.The vacuum ultraviolet phase-matching characteristics of nonlinear optical KBe2BO3F2crystal[J].Applied Physics Letters,1996,68(21):2930-2932.

WALSH A,PAYNE D J,EGDELL R G,et al.Stereochemistry of post-transition metal oxides:Revision of the classical lone pair model[J].Chemical Society Reviews,2011,40(9):4455-4463.

PAYNE D J,EGDELL R G,WALSH A,et al.Electronic origins of structural distortions in post-transition metal oxides:Experimental and theoretical evidence for a revision of the lone pair model[J].Physical Review Letters,2006,96(15):157403.

DONG X Y,JING Q,SHI Y J,et al.Pb2Ba3(BO3)3Cl:A material with large SHG enhancement activated by Pb-chelated BO3groups[J].Journal of the American Chemical Society,2015,137(29):9417-9422.

HUANG Y Z,WU L M,WU X T,et al.Pb2B5O9I:An iodide borate with strong second harmonic generation[J].Journal of the American Chemical Society,2010,132(37):12788-12789.

HAN S J,MUTAILIPU M,TUDI A,et al.PbB5O7F3:A high-performing short-wavelength nonlinear optical material[J].Chemistry of Materials,2020,32(5):2172-2179.

YANG Y,QIU Y,GONG P F,et al.Lone-pair enhanced birefringence in an alkaline-earth metal tin(II)phosphate BaSn2(PO4)2[J].ChemistryA European Journal,2019,25(22):5648-5651.

GUO J Y,TUDI A,HAN S J,et al.α-SnF2:A UV birefringent material with large birefringence and easy crystal growth[J].Angewandte Chemie International Edition,2021,60(7):3540-3544.

LIN C S,ZHOU A Y,CHENG W D,et al.Atom-resolved analysis of birefringence of nonlinear optical crystals by Bader charge integration[J].The Journal of Physical Chemistry C,2019,123(51):31183-31189.

JING Q,YANG Z H,PAN S L,et al.Contribution of lone-pairs to birefringence affected by the Pb(II)coordination environment:A DFT investigation[J].Physical Chemistry Chemical Physics,2015,17(34):21968-21973.

HELLWIG H,LIEBERTZ J,BOHATY L.Exceptional large nonlinear optical coefficients in the monoclinic bismuth borate BiB3O6(BIBO)[J].Solid State Communications,1998,109(4):249-251.

LIU Y C,LIU X M,LIU S,et al.An unprecedented antimony(III)borate with strong linear and nonlinear optical responses[J].Angewandte Chemie International Edition,2020,59(20):7793-7796.

HELLWIG H,LIEBERTZ J,BOHATY L.Linear optical properties of the monoclinic bismuth borate BiB3O6[J].Journal of Applied Physics,2000,88(1):240-244.

GUO J Y,TUDI A,HAN S J,et al.Sn2B5O9Cl:A material with large birefringence enhancement activated prepared via alkaline-earth-metal substitution by tin[J].Angewandte Chemie International Edition,2019,58(49):17675-17678.

GUO J Y,CHENG S C,HAN S J,et al.Sn2B5O9Br as an outstanding bifunctional material with strong second-harmonic generation effect and large birefringence[J].Advanced Optical Materials,2021,9(5):2001734.

陈兆慧，潘世烈，赵文武，等.非线性光学晶体Ba2B5O9Cl的合成、晶体生长及性能的研究[J].人工晶体学报，2011,40(6):1394-1398.CHEN Z H,PAN S L,ZHAO W W,et al.Study on synthesis,crystal growth and properties of nonlinear optical crystal Ba2B5O9Cl[J].Journal of Synthetic Crystals,2011,40(6):1394-1398.(in Chinese)

CHEN Z H,PAN S L,YANG Z H,et al.Pb2B5O9Cl:A chloride borate with second harmonic generation effect[J].Journal of Materials Science,2013,48(6):2590-2596.

EGOROVA B V,OLENEV A V,BERDONOSOV P S,et al.Lead-strontium borate halides with hilgardite-type structure and their SHG properties[J].Journal of Solid State Chemistry,2008,181(8):1891-1898.

PLACHINDA P A,DOLGIKH V A,STEFANOVICH S Y,et al.Nonlinear-optical susceptibility of hilgardite-like borates M2B5O9X(M=Pb, Ca,Sr, Ba; X=Cl, Br)[J].Solid State Sciences,2005,7(10):1194-1200.

LUO M,LIANG F,SONG Y X,et al.Rational design of the first lead/tin fluorooxoborates MB2O3F2(M=Pb, Sn),containing flexible two-dimensional[B6O12F6]∞single layers with widely divergent second harmonic generation effects[J].Journal of the American Chemical Society,2018,140(22):6814-6817.

SHI X R,JING Q,CHEN Z H,et al.Different mechanism of response of asymmetric lone pair electrons around ns2cations to birefringence and second harmonic generation[J].Journal of Applied Physics,2020,128(11):113104.

SIDGWICK N V,POWELL H M.Bakerian Lecture:Stereochemical types and valency groups[J].Proceedings of the Royal Society of London Series A,1940,176(965):153-180.

GILLESPIE R J,NYHOLM R S.Inorganic stereochemistry[J].Quarterly Reviews,Chemical Society,1957,11(4):339-380.

ORGEL L E.The stereochemistry of B subgroup metals.Part II.The inert pair[J].Journal of the Chemical Society,1959(0):3815-3819.

WATSON G W,PARKER S C,KRESSE G.Ab initio calculation of the origin of the distortion of α-PbO[J].Physical Review B,1999,59(13):8481-8486.

WATSON G W,PARKER S C.Origin of the lone pair of α-PbO from density functional theory calculations[J].The Journal of Physical Chemistry B,1999,103(8):1258-1262.

WALSH A,WATSON G W.Electronic structures of rocksalt,litharge,and herzenbergite SnO by density functional theory[J].Physical Review B,2004,70(23):235114.

WATSON G W.The origin of the electron distribution in SnO[J].Journal of Chemical Physics,2001,114(2):758-763.

ZHU Y,WU H,CUI X.Stereochemical activity of lone pair electrons in a class of metal halides and its effect on birefringence[J].Journal of Physics B:Atomic,Molecular and Optical Physics,2023,40(6):158-168.

FRISCH A.Gaussian 09W reference[M].Wallingford:Gaussian,Inc,2009.

CLARK S J,SEGALL M D,PICKARD C J,et al.First principles methods using CASTEP[J].Zeitschrift F¨ur Kristallographie-Crystalline Materials,2005,220(5/6):567-570.

WANG K,JING Q,WAN Z Z,et al.Different mechanism of stereochemical activity and birefringence in post-transition metal halides:A first-principles investigation[J].Journal of Solid State Chemistry,2021,297(1):122038.

SHI X R,JING Q,LEE M H,et al.A first-principle investigate about the different response of birefringence and SHG from AB3O6(A=Bi,Sb)compounds[J].Chemical Physics Letters,2022,786:139188.

QIAN Y Y,JING Q,DUAN H M,et al.First-principles study of the influence of lone pair electrons and molecular groups on the birefringence of phosphate and fluorophosphate[J].Physica B:Condensed Matter,2022,630:413676.

JING Q,YANG G,CHEN Z H,et al.A joint strategy to evaluate the microscopic origin of the second-harmonic-generation response in nonpolar ABCO3F compounds[J].Inorganic Chemistry,2018,57(3):1251-1258.

JING Q,YANG G,HOU J,et al.Positive and negative contribution to birefringence in a family of carbonates:A Born effective charges analysis[J].Journal of Solid State Chemistry,2016,244:69-74.

BECKE A D,EDGECOMBE K E.A simple measure of electron localization in atomic and molecular systems[J].The Journal of Chemical Physics,1990,92(9):5397-5403.

GIBBS G V,COX D F,BOISENJRM B,et al.The electron localization function:A tool for locating favorable proton docking sites in the silica polymorphs[J].Physics and Chemistry of Minerals,2003,30(5):305-316.

SAVIN A,NESPER R,WENGERT S,et al.ELF:The electron localization function[J].Angewandte Chemie International Edition in English,1997,36(17):1808-1832.

JU S,GUO G Y.First-principles study of crystal structure,electronic structure,and second-harmonic generation in a polar double perovskite Bi2ZnTiO6[J].The Journal of Chemical Physics,2008,129(19):194704.

ZHANG H,ZHANG M,PAN S L,et al.Na3Ba2(B3O6)2F:Next generation of deep-ultraviolet birefringent materials[J].Crystal Growth&Design,2015,15(1):523-529.

XIA Y N,CHEN C T,TANG D Y,et al.New nonlinear optical crystals for UV and VUV harmonic generation[J].Advanced Materials,1995,7(1):79-81.

LIN Z S,JIANG X X,KANG L,et al.First-principles materials applications and design of nonlinear optical crystals[J].Journal of Physics D:Applied Physics,2014,47(25):253001.

CHEN C T,WU Y C,JIANG A D,et al.New nonlinear-optical crystal:LiB3O5[J].Journal of the Optical Society of America B,1989,6(4):616-621.

OSELEDCHIK Y S,PROSVIRNIN A L,PISAREVSKIY A I,et al.New nonlinear optical crystals:Strontium and lead tetraborates[J].Optical Materials,1995,4(6):669-674.

SHANNON R D,FISCHER R X.Empirical electronic polarizabilities in oxides,hydroxides,oxyfluorides,and oxychlorides[J].Physical Review B,2006,73(23):235111.

QIN F L,LI R K.Predicting refractive indices of the borate optical crystals[J].Journal of Crystal Growth,2011,318(1):642-644.

LIN Z S,KANG L,ZHENG T,et al.Strategy for the optical property studies in ultraviolet nonlinear optical crystals from density functional theory[J].Computational Materials Science,2012,60:99-104.

NAHERM I,NAQIBS H.A comprehensive study of the thermophysical and optoelectronic properties of Nb2P5via ab-initio technique[J].Results in Physics,2021,28:104623.

BIAN Q,YANG Z H,DONG L Y,et al.First principle assisted prediction of the birefringence values of functional inorganic borate materials[J].The Journal of Physical Chemistry C,2014,118(44):25651-25657.

XU K,LOISEAU P,AKA G,et al.Nonlinear optical properties of Ca5(BO3)3F crystal[J].Optics Express,2008,16(22):17735-17744.

HU C L,XU X,SUN C F,et al.Electronic structures and optical properties of Ca5(BO3)3F:A systematical first-principles study[J].Journal of Physics:Condensed Matter,2011,23(39):395501.

BOHATY L,OCHROMBEL R,LIEBERTZ J,et al.Linear electrooptic effect of the monoclinic polar bismuth triborate,BiB3O6[J]. Crystal Research and Technology,2017,52(1):1600250.

JING Q,DONG X Y,YANG Z H,et al.The interaction between cations and anionic groups inducing SHG enhancement in a series of apatite-like crystals:A first-principles study[J].Journal of Solid State Chemistry,2014,219:138-142.

MORRIS A J,NICHOLLS R J,PICKARD C J,et al.OptaDOS:A tool for obtaining density of states,core-level and optical spectra from electronic structure codes[J].Computer Physics Communications,2014,185(5):1477-1485.

NICHOLLS R J,MORRIS A J,PICKARD C J,et al.OptaDOS:A new tool for EELS calculations[J].Journal of Physics:Conference Series,2012,371:012062.

YATES J R,WANG X J,VANDERBILT D,et al.Spectral and Fermi surface properties from Wannier interpolation[J].Physical Review B,2007,75(19):195121.

ZHOU G Q,XU J,CHEN X D,et al.Growth and spectrum of a novel birefringent α-BaB2O4crystal[J].Journal of Crystal Growth,1998,191(3):517-519.

NIKOGOSYAN D N.Nonlinear optical crystals:A complete survey[M].Berlin:Springer,2005.

HUANG H W,CHEN C T,WANG X Y,et al.Ultraviolet nonlinear optical crystal:CsBe2BO3F2[J].Journal of the Optical Society of America B,2011,28(9):2186-2190.

ZHAI N X,WANG L R,LIU L J,et al.Measurement of thermal refractive index coefficients of nonlinear optical crystal RbBe2BO3F2[J].Optical Materials,2013,36(2):333-336.

WANG X,XIA M J,LI R K.A promising birefringent crystal Ba2Na3(B3O6)2F[J].Optical Materials,2014,38:6-9.

XU K,LOISEAU P,AKA G,et al.A new promising nonlinear optical crystal for ultraviolet light generation:Ca5(BO3)3F[J].Crystal Growth&Design,2009,9(5):2235-2239.

LIN J,LEE M H,LIU Z,et al.Mechanism for linear and nonlinear optical effects in β-BaB2O4crystals[J].Physical Review B,1999,60(13):13380.

SPALDIN N A.A beginner′s guide to the modern theory of polarization[J].Journal of Solid State Chemistry,2012,195:2-10.

WANG C,YU R,KRAKAUER H.Polarization dependence of Born effective charge and dielectric constant in KNbO3[J].Physical Review B,1996,54:11161.

MANCHON A,KOO H C,NITTA J,et al.New perspectives for Rashba spin-orbit coupling[J].Nature Materials,2015,14(9):871-882.

NARSIMHA R E,VAITHEESWARAN G,RESHAK A H,et al.Role of spin-orbit interaction on the nonlinear optical response of CsPbCO3F using DFT[J].Physical Chemistry Chemical Physics,2017,19(46):31255-31266.

JIANG X,YE L T,WU X Q,et al.Role of large Rashba spin-orbit coupling in second-order nonlinear optical effects of polar BiB3O6[J].Physical Review B,2022,106(19):195126.

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