Structural and Optical Properties of Point Defects in α-SiO2 Cluster

First-principles methods based on the density functional theory (DFT) are used in order to calculate the structural and optical properties of α-SiO₂ cluster with the non-bridging oxygen hole centers (NBOHC) and NBOHC-E' defects. We clarify the stable structure of the NBOHC-E' point defects for the first time using the functional B3LYP, which is also tested to investigate the influence of electronic properties. The calculation is carried out for cluster configurations extracted from supercell. The results of optical absorption peak for Si₂O₇H₆ and Si₅O₁₆H₁₂ with NBOHC-E' defects are found at 2.66 eV, which is higher than the often observed OA peak at 2.0 eV for the NBOHC defect in α-SiO₂. The overall absorption spectra are in qualitative agreement with the experiment.     

Mn、Fe掺杂ZnS的第一性原理计算

采用基于密度泛函理论(DFT)的第一性原理平面波超软赝势方法,计算了闪锌矿结构的纯净ZnS、Mn掺杂ZnS和Fe掺杂ZnS的电子结构和光学性质,分析了掺杂对ZnS晶体的能带结构、电子态密度、光学吸收系数的影响。计算结果表明:掺杂体系费米能级附近的电子态密度主要来源于Mn 3d,Fe 3d态电子的贡献;Mn、Fe掺杂情况下的光吸收谱均向低能级方向移动且在低能端形成新的吸收峰,红移效应明显。     

Stress and strain effects on the electronic structure and optical properties of ScN monolayer

Based on the density functional theory, electronic and optical properties of a monolayer scandium nitride structure have been studied under different strain conditions. Our results indicate that both biaxial compressive and tensile strain effects lead to change the band gap of this structure with different rates. Also, optical absorption spectrum peaks experience an obvious red and blue shifts with the exerting of tensile and compressive strains, respectively. Our results express that ScN monolayer can be the promising candidate for the future nano-base electrical and optical devices.     

第一性原理研究Fe掺杂SnO2材料的光电性质

采用基于第一性原理的线性缀加平面波(FP-LAPW)方法,研究Fe掺杂SnO₂材料电子结构和光学性质,包括电子态密度、能带结构、介电函数和其他一些光学图谱. 研究结果表明,掺Fe后材料均属于直接跃迁半导体,且呈现半金属性;随掺杂浓度增加,费米能级进入价带,带隙逐渐减小,Fe原子之间耦合作用增强;通过掺杂能够在一定程度上改变成键性质,使其具有金属键性质. 光学谱线(吸收谱、消光系数等)与介电函数虚部谱线相对应,均发生蓝移,各峰值与电子跃迁吸收有关,从理论上指出光学性质和电子结构的内在联系. 关键词： 能带结构 态密度 光学性质 介电函数     

Fe和Ni共掺杂ZnO的电子结构和光学性质

基于密度泛函理论的第一性原理研究Fe,Ni单掺杂和(Fe,Ni)共掺杂纤锌矿型ZnO的能带结构、电子态密度分布、介电函数、光学吸收系数,分析了掺杂后电子结构与光学性质的变化.计算结果表明：掺杂体系的费米能级附近电子态密度主要来源于Fe 3d,Ni 3d态电子的贡献;与纯净ZnO相比,Fe,Ni单掺杂和(Fe,Ni)共掺杂ZnO的介电函数虚部均在0.46eV左右出现了一个新峰;Fe,Ni单掺杂和共掺杂ZnO的吸收光谱均发生明显的红移,并都在1.3eV处出现较强吸收峰.结合他人的计算和实验结果,给出了定性的讨 关键词： 氧化锌 掺杂 第一性原理 光学性质     

Simultaneous Effects of External Electric Field and Conduction Band Nonparabolicity on Optical Properties of a GaAs Quantum Dot Embedded at the Center of a GaAlAs Nano-Wire

An investigation of the optical properties of a GaAs spherical quantum dot which is located at the center of a Ga1-xAlx As cylindrical nano-wire has been performed in the presence of an external electric field. The band nonparabolieity effect is also considered using the energy dependent effective mass approximation. The energy eigenvalues and corresponding wave functions are calculated by finite difference approximation and the reliability of calculated wave functions is checked by computing orthogonality. Using computed energy eigenvalues and wave functions, the linear, third-order nonlinear and total optical absorption coefficients and refractive index changes are examined in detail. It is found that （i） Presence of electric field causes both blue and red shifts in absorption spectrum; （ii） The absorption coefficients shift toward lower energies by taking into account the conduction band nonparabolicity; （iii） For large values of electric field the effect of conduction band nonparabolieity is less dominant and parabolic band is estimated correctly; （iv） In the presence of electric field and conduction band nonparabolicity the nonlinear term of absorption coefficient rapidly increases by increasing incident optical intensity. In other words, the saturation in optical spectrum occurs at lower incident optical intensities.     

熔石英中过氧缺陷及中性氧空位缺陷的几何结构、电子结构和吸收光谱的准粒子计算

本文使用密度泛函理论研究了熔石英中peroxy linkage(POL)缺陷和中性氧空位(NOV)缺陷的几何结构,电子结构以及光学性质.采用自洽的准粒子GW计算结合求解Bathe-Salpeter方程的多体理论,研究了缺陷引起的电子结构和光学吸收谱的变化.首先研究了无缺陷非晶结构的电子结构与吸收谱,得到的结果与实验值非常接近.对POL的计算表明,其在基态下的局部结构与过氧化氢分子类似.采用多体理论计算得到的吸收谱表明其最低吸收峰位于6.3 eV处.这一结果不支持实验认为的位于3.8 eV处的吸收峰是由POL缺陷导致的说法.对于NOV缺陷,计算表明其基态的Si—Si键长为2.51?而三重态下的值则为3.56?.相应的GW+BSE计算表明中性氧空位缺陷导致了位于7.4 eV处的吸收峰,与实验测量结果一致.     

Fe,Ni掺杂CdS的电子结构和光学性质

基于密度泛函理论（DFT）的第一性原理研究了Fe,Ni单掺杂和（Fe,Ni）共掺杂CdS的能带结构、电子态密度分布、介电常数和光学吸收系数,分析了掺杂后电子结构和光学性质的变化.计算结果表明:掺杂体系的CdS晶格常量均减少,能带宽度减小,介电函数虚部ε₂（ω）都在0.53 eV左右出现了一个新峰,吸收光谱发生明显的红移,它们均在1.35 eV处出现较强吸收峰.     

Linear and nonlinear optical properties of strained GaN/AlN quantum dots: Effects of impurities,radii of QDs,and the incident optical intensity

The linear and nonlinear optical properties of cylinder GaN/AlN quantum dots with strain effects and impurity are investigated by taking into account the effects of the deformation potential and piezoelectric potential on the conduction band edge. The results are presented as a function of photon energies and QD radii. The optical absorption spectrum and refractive index changes have a blueshift in the presence of the impurity. With increasing distance of the impurity’s position along the growth direction, the peak values of the refractive index changes decrease and shift to higher photon energy. When the sizes of the QDs increase, redshift effects are observed and the relative amplitudes diminish. It can be found that the nonlinear effect becomes obvious with increase of the incident optical intensity. Then there is a “hole-burning” in the absorption coefficient spectra and two new peaks will appear in the total refractive index change spectrum when the optical intensity becomes larger enough. Finally it can be concluded that the intensity of the incident light and the position of the impurity play an important role in the linear and nonlinear optical properties.     

Na_2Ge_2Se_5电子结构和光学性质的第一性原理研究

Na_2Ge_2Se_5是一种优异的红外非线性晶体材料.采用基于第一性原理的密度泛函理论赝势平面波方法对Na_2Ge_2Se_5进行结构优化,并以此为基础计算研究了Na_2Ge_2Se_5的电子结构和光学性质.结果表明:Na2Ge2Se5是宽禁带间接带隙半导体,价带至导带的电子跃迁主要来自于Ge和Se的48,4p态;Na对光学性质的贡献较小,Ge和Se之间的相互耦合作用决定了Na_2Ge_2Se_5的光学性质;该晶体在紫外区有强烈的反射和吸收,静态折射率为2.133,双折射率值适中,为0.145.理论计算结果表明,Na_2Ge_2Se_5是一种性能优良的红外非线性光学晶体材料.     

X射线辐照后BaFC1中缺陷性质的研究

未掺Eu2+的BaFCl粉末样品在80K下经X射线辐照后,在不同的温度条件下(从80K副273K),用580nm的光波激励样品时观测到310nm和380nm的发光峰.经分析认为,样品经X射线辐照后,在晶体中形成两种卤素离子的F-H''心对.当用F心吸收带的光波激励样品时,两种F—H心对衰变成相应的自陷激子态并复合发光.310nm和380nm分别对应于F-离子和Cl-离子的自陷激子的发光,并且它们的发光强度强烈地依赖于温度的变化。     

An EPR study of optical absorption of the oxygen-vacancy pair in electron-irradiated silicon

The negative charge state of the vacancy-oxygen pair (Si-B1) in irradiated silicon was populated by illumination with polarized light, from which the direction of the electric dipole moment was determined to be near 〈110〉 perpendicular to the (Si-O-Si) bond axis. Energy dependence of the alignment suggests the presence of an optical absorption band at λ = 1.30 μm.     

Band engineering of silicon for light emission: First-principles approach to the effect of co-doping with nitrogen and fluorine

A Si-based light emitter has long been the final key component for electronic and photonic integrated circuits on Si, because Si has an indirect band gap. Atomistic and electronic structures and energy gains of formation of possible nitrogen (N) and fluorine (F) complexes in Si have been researched from first-principles, in order to engineer the band structure of Si for light emission. The calculated results show that the substitutional nitrogen N_S and bond center fluorine F_BC pair complex has large stabilization energy, and that the pair-complex-doped Si has direct band gap, which is reduced with respect to that of Si. These results lead to the possibilities of doping-based engineering of Si optical properties with introduction of deep-level impurity and charge compensation.     

Electronic structure of oxygen dangling bond in glassy SiO2: the role of hyperconjugation

The electronic structure and the nature of optical transitions in oxygen dangling bond in silica glass, the nonbridging oxygen hole center (NBOHC), were calculated. The calculation reproduced well the peak positions and oscillator strengths of the well-known optical absorption bands at 2.0 and 4.8 eV, and of the recently discovered absorption band at 6.8 eV. The 2.0 eV band was attributed to transition from the sigma bond between Si and dangling oxygen to nonbonding pi orbital on the dangling oxygen. The uniquely small electron-phonon coupling associated with the 2.0 eV transition is explained by stabilization of Si-O bond in the excited state by hyperconjugation effects.     

KH_2PO_4晶体的太赫兹-紫外光谱

实验测量了室温下磷酸二氢钾KH2PO4(KDP)晶体0.2～1.6THz的时域光谱,以及50～4000cm-1范围内的远红外光谱,200～2000nm的紫外-可见-红外光谱。KDP晶体的禁带宽度是5.91eV。在测量范围内有一个很宽的声子吸收带。从0.2～205.5THz吸收系数在35～80cm-1,声子吸收的低频端小于0.2THz。最高的纵光学模声子的频率νLO大约是205.5THz,由此求出这支声子的H—O键的力常数为13.13N·cm-1。     

Photocleavage reaction of bromine substituted aromatic acyl compounds studied by CIDEP and transient absorption spectroscopy

The photocleavage of the CBr bond in bromoacetylnaphthalene is investigated by transient absorption and time resolved EPR spectroscopy. In the transient absorption of 2-bromo-2′-acetylnaphthalene, the absorption band observed at λ_max ~440 nm is assigned to the triplet state of the parent molecule. After decay of the triplet absorption, a long lived absorption band is observed at λ_max ~380 nm, which is assigned to naphthoylmethyl radical. The yield of this radical is not dependent on the concentration of oxygen even though the absorption band of the triplet state was quenched by addition of oxygen. Thus we conclude that the spin multiplicity of the precursor molecule is singlet. The CW time resolved EPR spectrum shows a typical E?/A CIDEP pattern of three hyperfine lines of the naphthoylmethyl radical. This result suggests some contribution from triplet precursor molecules. However, a careful analysis of the time profile of the CIDEP intensity observed by FT-EPR revealed that the polarization is generated from the radical pair mechanism (RPM) from the encountered pair of two free naphthoylmethyl radicals and the radical-triplet pair mechanism. RPM polarization by the geminate radical pair, formed by the Br atom and the naphthoylmethyl radical, is not observed. This fact indicates that large spin-orbit coupling (Δg and/or fast spin relaxation by g anisotropy) spoils the RPM polarization. The finding is in contrast to the recent observation of RPM polarization in the Cl cleavage reaction of 1-(chloromethyl)naphthalene.     

第一性原理研究缺陷对高压下LiF的电子结构和光学性质的影响

基于密度泛函理论下的平面波超软赝势方法,本文计算了102 GPa压力下LiF理想和含空位（Li-1 、F+1）晶体的电子结构和光学性质.结果表明:102 GPa压力下理想LiF晶体有良好的透明性;高压下Li-1及F+1两种空位的存在不影响LiF的光学透明性.分析其原因：LiF是一种带隙很宽的离子晶体,电子发生跃迁需要较高的能量; LiF中F元素的电负性很大,Li的电负性却很小,二者结合的Li-F键键能很高.另外本文还计算了102 GPa压力下理想LiF晶体及Li-1 、F+1两种空位分别存在时的反射、折射率、介电函数和光损失函数等一些光学性质,并将理想和含空位的做了比较,结果表明：102 GPa压力下空位的存在对LiF在可见光范围内这些光学性质都不产生影响,但由于F+1空位的存在使LiF晶体对光的吸收发生了红移现象.     

Tailoring the photocatalytic activity of WO3 by Nb-F codoping from first-principles calculations

In this letter, the electronic structure properties of Nb, F monodoping and Nb-F codoping are explored by first-principles calculations. Our results show that Nb-F codoping can reduce the band gap notably. The band edge analysis indicates that both conduction band maximum (CBM) and valence band minimum (VBM) move to higher energies, which is desirable for water splitting. The formation energy and pair binding energy calculation shows that this anion-cation codoping is easy to realize in both O-rich and O-poor conditions. The calculated optical absorption spectra indicate that the visible light absorption can be significantly improved by Nb-F codoping in WO₃. Therefore, Nb-F co-doped WO₃ is predicted to be a promising visible light photocatalyst for water splitting.     

First-principles study on the optical properties for CsI crystal with a pair of V_(Cs)~(1-)-V_I~(1+)

The electronic structures and optical properties of both the perfect CsI crystal and the crystal containing a pair of V_(Cs)~1-V_1~(1+) are calculated using CASTEP code with the lattice structure optimized.The calculated results indicate that the optical symmetry of the CsI crystal coincides with the lattice structure geometry of the CsI crystal.The absorption spectrum of the CsI crystal containing a pair of V_(Cs)~(1-)-V_1~(1+) also does not occur in the visible and near-ultraviolet range.It reveals tha...     

基于密度泛函理论的肾上腺素分子的光谱分析

肾上腺素是一种神经和激素的传送体,研究肾上腺素分子的光谱和能级有助于了解其化学稳定性和药理作用。基于密度泛函理论（DFT）,利用Gaussian 09软件在B3LYP/6-311G（d,p）基组水平上对肾上腺素分子进行结构优化,采用含时密度泛函理论（TD-DFT）的PBE方法在def2tzvp基组水平上计算肾上腺素分子在气相中的前20个激发态,利用Multiwfn3.7（dev）软件绘制出其紫外光谱图并对激发性质进行分析。肾上腺素分子紫外光谱对应的主要跃迁是从基态分别到第1,2,4,8,15和16激发态的跃迁,其他的激发态的振子强度低于阈值0.03。理论计算得出肾上腺素的紫外光谱有两个吸收峰,分别位于206.23和273.92 nm,206.23 nm峰主要由基态跃迁到第16激发态形成,273.92 nm峰主要是基态跃迁到第2、4激发态形成,主要是由苯环上π→π*跃迁所产生,并与实验光谱吻合较好。对肾上腺素分子的激发态性质分析可知,上述吸收峰都是在最高占据轨道和最低空轨道的临近轨道跃迁产生的。利用密度泛函的PBE方法在6-311G（d, p）的基组水平上计算肾上腺素分子频率并绘制红外光谱,由振动分析可知,3 738和3 662 cm-1峰是由酚羟基O-H伸缩振动产生的特征吸收峰,3 715 cm-1峰是由醇羟基O-H伸缩振动产生的特征吸收峰,2 854 cm-1峰是由甲基的C18-H20键的伸缩振动产生的特征吸收峰,1 516和1 439 cm-1峰是苯环骨架的伸缩振动的特征吸收峰,1 279与1 057 cm-1峰分别是由C6-O10和C12-O23键伸缩振动产生的特征吸收峰,620 cm-1峰是N22-H17键摇摆振动的特征吸收峰。对比肾上腺素的实验红外光谱,发现理论光谱与实验光谱中各基团的特征吸收峰都较为明显且总体吻合较好。由于肾上腺素分子二聚体和多聚体之间形成氢键,分子间氢键的形成削弱了O-H键的强度,降低了能形成分子间氢键的羟基O-H的伸缩振动频率,从而导致实验光谱在3 500～2 500 cm-1之间呈现出一个宽峰。