非晶态合金Fe80P20局域结构和性质的量子化学研究

利用原子簇模型Fe_4P简化了非晶态合金Fe_(80)P_(20)的局域结构,设计了四方锥、三角双锥、四面体及平面五边形等十几种构型,对其二、四重态分别进行密度泛函(DFT)优化计算,经过频率验证,获得五种稳定构型。从所得优化构型的键长和键级,可以发现原子簇Fe4P较好地反映了非晶态合金Fe_(80)P_(20)的局域结构。考察了各构型间的过渡转化情况,发现二重态构型的稳定性要好于四重态。分析各构型的能量、成键及电子转移情况,发现与P原子成键的Fe原子个数对这些性质影响较为明显。与P原子成键的Fe原子个数越多,体系的能量就越低,越容易存在；P原子的得电子能力随着与其成键Fe原子个数增多而减少,甚至会将失去自身电子转移到金属原子上。同时通过3d轨道布居数,讨论了原子簇的空穴数及磁学性质。     

二苯二硫和二苄二硫润滑性能的量子化学研究

用Gaussian03W程序在B3LYP/631G和HF/631G水平上对二苯二硫(DPDS)和二苄二硫(DBDS)的分子几何构型、电子结构、分子轨道指数及与铁原子簇的相互作用等进行了理论计算.用前线分子轨道理论分析了反应的活性原子和活性键,讨论了DPDS和DBDS与铁原子的作用方式,用前线电子密度,超离域性指数,原子净电荷及化合物与铁原子簇的化学吸附作用能等参数作为判据分析了DPDS和DBDS与铁原子间键合的强弱,反应性的大小.计算结果表明DPDS和DBDS与铁接触时,趋向于S-S键与C-S键断裂,在较为缓和的摩擦条件下,DPDS的抗磨作用优于DBDS,在较为苛刻的摩擦条件下,DBDS的极压作用优于DPDS,与摩擦学试验结果一致.     

NnHn(n=3~7)氮氢化合物的结构与性质理论研究

本文对53种NnHn(n=3~7)氮氢化合物进行了理论计算，应用自然键轨道理论(Nature Bond Orbital, NBO)和分子中的原子理论(Atoms In Molecules, AIM)分析了化合物的成键特征、相对稳定性。氮原子孤对电子与氮氮键以及氮氮键相互之间的超共轭作用是影响氮氮键长的重要因素。采用原子基团法，比较了化合物的原子基团能量和原子基团生成热。通过预测53种化合物的稳定性，找出了氮氢化合物的稳定性与结构之间的一些规律，为预测氮氢化合物的稳定性提供了新的方法和新的数据。     

NnHn(n=3～7)氮氢化合物的结构质理论研究

本文对53种NnHn(n=3～7)氮氢化合物进行了理论计算,应用自然键轨道理论(Nature Bond Orbital,NBO)和分子中的原子理论(Atoms In Molecules,AIM)分析了化合物的成键特征、相对稳定性.氮原子孤对电子与氮氮键以及氮氮键相互之间的超共轭作用是影响氮氮键长的重要因素.采用原子基团...     

密度泛函理论研究硫族元素取代对单层Ag2S结构和电子性质的影响

本文利用第一性原理计算讨论了硫族元素掺杂单层Ag₂S的缺陷形成能和电子性质.缺陷形成能反映了在富Ag条件下的掺杂更容易.计算得到的带隙、Mulliken布居和态密度展示出了其相应结构的电子性质.与纯单层的Ag₂S相比,Se/Te掺杂Ag₂S后的带隙显示出其电导率变化不大.基于Mulliken原子和键布居,研究了硫族元素掺杂后Ag₂S中的共价性.此外,通过讨论态密度,分析了能级的移动和电子的贡献.     

低能原子簇轰击金属簿膜引起的级联碰撞(Ⅱ)——注入簇原子的加速

研究了能量为１ｋｅＶ／ａｔｏｍ的金原子簇和０．２ｋｅＶ／ａｔｏｍ的铝原子簇轰击金薄膜产生的级联碰撞。用分子动力学模拟计算了注入靶后的簇原子能量分布及其随时间的演化。结果表明，在原子簇注入引起的级联碰憧中，簇原子除了将能量传递给靶原子外，尚有可能破加速。簇原子的最高能量可大于它的初始能量；分析了原子簇注入引起的多次碰撞效应，并用经典力学守恒定律计算了一个簇原子发生二次散射后的能量增益，用以解释注入原子的加速机制。 关键词：     

用ARUPS和HREELS研究GaP(111)面的表面态

本文利用角分辨紫外光电子能谱(ARUPS)和高分辨率电子能量损失谱(HREELS)研究Ar⁺刻蚀退火处理的GaP(111)面表面态。发现与P原子悬挂键有关的本征满表面态在Г点位于价带顶下0.6eV处,而缺陷引入的空表面态位于价带顶上1.1eV处(Г点)。空表面态引起n型样品表面能带发生1.36eV弯曲。     

Photoelectron Spectroscopy, Photoionization Mass Spectroscopy, and Theoretical Study on CCl3SSCN

通过一种简单的方式产生了CCl3SSCN,并利用光电子能谱(PES)和光电离质谱(PIMS)对该化合物进行了表征．通过理论计算得知, 该分子围绕S－S键的二面角为91.4 o ． 这种扭曲结构是S－S键上的孤对电子的相互作用导致的．电离后基态的自由基离子CCl3SSCN￠+呈平面的反式构象(δCSSC=180o),且具有Cs对称性．CCl3SSCN分子的最高占据轨道(HOMO)为硫原子的3p孤对电子轨道：3pπf51a(nS(CCl3S))g-1. 实验得到的该分子的第一垂直电离能为10.40 eV．     

氮流量在高氢氛围中对富硅氮化硅薄膜材料结构及其发光特性的影响

采用等离子体增强化学气相沉积技术,以N₂掺入到SiH₄和H₂的沉积方式,分别在玻璃和N型单晶硅片(100)衬底上制备富硅氮化硅薄膜。通过紫外-可见光吸收光谱、傅里叶变换红外吸收光谱(FTIR光谱)、拉曼光谱和光致发光谱(PL谱)分别表征掺氮硅薄膜材料的带隙、结构及其发光特性的变化。结果表明：在氢气的氛围中,随着氮气流量的增加,氢原子能够对薄膜缺陷起到抑制作用,并使较低的SiH₄/N₂流量比下呈现富硅态,但却不利于硅团簇的形成。随着氮原子的掺入,Si—N键的含量增大,带隙增大,薄膜内微结构的无序度也增大,薄膜出现了硅与氮缺陷相关的缺陷态发光;随着氮原子进一步增加,出现了带尾态发光,进一步讨论了发光与结构之间的关联。这些结果有助于采用PECVD制备富硅氮化硅对材料发光与结构特性的优化。     

氧、硫掺杂六方氮化硼单层的第一性原理计算

采用基于密度泛函理论和投影缀加平面波的第一性原理计算方法, 研究了六方氮化硼单层(h-BN)中的氮原子缺陷(V_N)、氧原子取代氮原子(O_N)和硫原子取代氮原子(S_N)时的几何结构、磁性性质和电子结构.研究发现, V_N和O_N体系形变较小, 而S_N体系形变较大; h-BN本身无磁矩, 但具有N缺陷或者掺杂后总磁矩都是1 μ_B; 同时给出了态密度和能带结构.利用掺杂体系的局域对称性和分子轨道理论解释了相关结果, 尤其是杂质能级和磁矩的产生. 关键词： 六方BN单层 第一性原理计算 密度泛函理论 分子轨道理论     

A. C. conductivity due to intimate pairs of charged defect centres

The influence of the association of charged defects into intimate pairs on a.c. conduction is discussed in the light of the fundamental mechanism being that of the simultaneous hopping of two electrons over the barrier separating two oppositely charged defect centres, the barrier height being correlated with the intersite separation via the Coulomb interaction. The behaviour of chalcogenide glasses is discussed in terms of the present theory, and it is concluded that the existence of two classes of a.c. conductivity behaviour into which these materials generally fall can be simply explained by the predominance of either intimate pairs or non-intimate pairs of charged defect states according to the conditions of preparation.     

Non-radiative recombination in chalcogenide glasses

Non-radiative recombination of electron-hole pairs in chalcogenide glasses is described using a mechanism of a strong electron-phonon coupling. Recombination proceeds through a transient bonding rearrangement that creates a defect similar to those giving localized electronic states. Incomplete recombination which leaves the defect in a metastable state explains the reversible photostructural change.     

On a.c. conductivity in chalcogenide glasses

A simple model describing doubly occupied defect states in chalcogenide glasses is used to get the power frequency dependence of a.c. conductivity. The temperature dependence of the exponent is found to be linear for not too low temperatures.     

On the super-linear frequency dependent conductivity of amorphous semiconductors

A super-linear frequency dependent conductivity has been observed experimentally in several amorphous semiconductors. An explanation for this behaviour is proposed, in particular for the case of chalcogenide glasses, where it is shown to be a consequence of a particular spatial probability distribution for charged centres. The fundamental mechanism for a.c. conduction in chalcogenide glasses is the same as that proposed previously; namely, the simultaneous hopping of two electrons over the barrier separating two oppositely charged centres, the barrier height being correlated with the intersite separation via the Coulomb interaction. It is demonstrated that this phenomenon should be most marked in those glasses having a large band-gap.     

Radiation-Induced Coordination Topological Defects in Chalcogenide Glasses

The radiation-induced (γ-quanta of ⁶⁰Co source) coordination topological defect formation in chalcogenide glasses of quasi-binary AS₂S₃—GeS₂ system is studied using experimental techniques of IR Fourier spectroscopy and positron annihilation lifetime measurements. The new model of open-volume microvoids connected with negatively charged under-coordinated defects is developed at the basis of the obtained results.     

Photoinduced stable second-harmonic generation in chalcogenide glasses

We report on photoinduced second-harmonic generation (SHG) in chalcogenide glasses. Fundamental and second-harmonic waves from a nanosecond pulsed Nd:YAG laser were used to induce second-order nonlinearity in chalcogenide glasses. The magnitude of SHG in 20G?20A?60S glass was 10(4) larger than that of tellurite glass with a composition of 15Nb(2)O (5) 85TeO(2) (mol.%). Moreover, no apparent decay of photoinduced SHG in 20G?20A?60S glass was observed after optical poling at room temperature. We suggest that the large and stable value of chi((2)) is due to the induced defect structures and large chi((3)) of the chalcogenide glasses.     

Structure and formation mechanism of Ge E (') center from divalent defects in Ge-doped SiO2 glass

We have performed ab initio quantum-chemical calculations on clusters of atoms modeling a divalent Ge defect in Ge-doped SiO (2) glasses. It has been found that the divalent Ge defect interacts with a nearby GeO (4) tetrahedron, forming complex structural units that are responsible for the observed photoabsorption band at approximately 5 eV. We have shown that these structural units can be transformed into two equivalent Ge E' centers by way of the positively charged defect center.     

New type of charged defect in amorphous chalcogenides

We report on density-functional-based tight-binding simulations of a series of amorphous arsenic sulfide models. In addition to the charged coordination defects previously proposed to exist in chalcogenide glasses, a novel defect pair, [As(4)](-)-[S(3)](+), consisting of a fourfold coordinated arsenic site in a seesaw configuration and a threefold coordinated sulfur site in a near-planar trigonal configuration, was found in several models. The valence-alternation pairs [S(3)](+)-S-1 are converted into [As(4)](-)-[S(3)](+) pairs under HOMO-to-LUMO electronic excitation. This structural transformation is accompanied by a decrease in the size of the HOMO-LUMO band gap, which suggests that such transformations could contribute to photodarkening in these materials.     

Photoconductivity in amorphous chalcogenide thin films: Effect of incorporation of Bi,Sb and Te IN Ge22Se78 binary alloy

Temperature and intensity dependence of steady state photoconductivity is studied in amorphous thin films of various chalcogenide glasses with a view to see the effect of incorporation of Bi, Sb and Te in Ge-Se system. Our results show that the photosensitivity decreases as 10 at % of Bi, Sb and Te are incorporated in Ge₂₂Se₇₈.Transient photoconductivity measurements have also been made on the same samples. These results show that the decay of photoconductivity becomes slower when Bi, Sb and Te are incorporated. The results have been explained in terms of the defect states which are introduced after incorporation of these elements in the binary system.     

Photo-induced nonthermal melting of amorphous chalcogenides observed by pump and probe x-ray absorption spectroscopy

A new kind of melting phenomenon which is not based on thermal excitation has been observed. X-ray absorption spectroscopy (XAS) experiments under optical pumping provide a “snap-shot” information on the local structure under excitation. We have studied the local structure of chalcogenide glasses such as vitrious selenium and As₂Se₃ under optical excitation and confirmed the local melting phenomenon under light illumination at low temperature. The photo-induced nonthermal melting (PNM) in chalcogenide glasses is interpreted as the result of pairing of excited lone pair electrons during the illumination. Trapped states in this photo-assisted metastable phase result in a local structural disorder which is partially quenched at room temperature. The increased short-range disorder causing Coulomb repulsion is the origin of red shift of the absorption coefficient known as the photodarkening effect. We found that the bond alternation of chalcogens occurs during the photo-excitation.