锆掺杂二氧化铀中氧缺陷扩散机制的密度泛函计算研究

应用基于量子力学的密度泛函计算和过渡态搜寻的CI-NEB方法,研究了锆掺杂前后二氧化铀晶格中氧空位和氧间隙本征缺陷的扩散机理,计算了扩散路径和扩散能垒。计算结果表明,锆掺杂使得氧空位缺陷<100>方向的扩散能垒降低了0.40 eV,氧间隙交换机制的扩散能垒降低了0.07 eV。锆掺杂后,氧空位远低于氧间隙缺陷的扩散能垒。最后分析了扩散过程中氧原子和金属原子之间的键长,说明锆掺杂导致点缺陷扩散能垒降低与晶格畸变密切相关。Oxygen vacancy and interstitial diffusion mechanisms in uranium dioxide doped with zirconium are investigated by the density functional theory calculations. The migration pathways and barriers are identified using the climbing-image nudge elastic band (CI-NEB) method. It is found that the vacancy migration barrier along the <100> direction decreases by about 0.40 eV, while the indirect interstitial migration barrier decreases by about 0.07 eV in the zirconium doped uranium dioxide. The oxygen vacancy migration barrier is far lower than the oxygen interstitial migration barrier in the uranium dioxide doped with zirconium. Based on the analysis of bond length of local structures during the migration of oxygen atoms, it is concluded that the lattice distortion may be responsible for the reduction of oxygen migration barrier.     

金红石TiO_2本征缺陷磁性的第一性原理计算

基于密度泛函理论的平面波超软赝势方法模拟计算了金红石相TiO_2的四种本征缺陷(氧空位、钛空位、钛间隙缺陷、氧间隙缺陷)和两种复合缺陷(氧空位与氧间隙复合缺陷、钛空位与钛间隙复合缺陷)的铁磁特性.结合态密度、电子分布及晶体结构变化分析可知,四种本征缺陷均会在系统内引入缺陷态.氧空位、钛间隙缺陷使费米面升高,引起自旋极化,引入磁矩分别为1.62μB与3.91μB;钛空位的缺陷态处于价带顶,使费米面进入价带,表现出明显的p型半导体特性,引入磁矩约为2.47μB;氧间隙缺陷引入缺陷态但仍然处于自旋对称状态,费米面略微下降;氧空位与氧间隙复合缺陷使费米面上升的程度比单个氧空位时大,模拟的超晶胞保持了氧空位的铁磁特性,大小为1.63μB;钛空位与钛间隙复合缺陷以反铁磁方式耦合,但超晶胞仍具有一定的铁磁特性.     

金红石型TiO_2中四种点缺陷态研究

利用第一性原理计算方法研究了金红石型TiO_2中四种缺陷的电子态.这四种缺陷包括氧空位(O_v)、钛空位(Ti_V)、钛间隙(Ti_S)以及氧空位O_v与钛间隙态Ti_S共存态.氧空位的存在导致禁带内施主缺陷能级较浅,而深施主能级与Ti间隙态有关.预测了氧空位更倾向于与钛间隙结合,主要通过钛间隙态的3d电子部分转移到近邻近氧空位的部分形成O_V-Ti_S对缺陷.具有O_v、Ti_S或O_V-Ti_S缺陷的体系都出现间隙态,促进体系出现红外吸收.     

H在Ni表面的扩散性质及表面缺陷的影响-嵌入原子法(EAM)计算研究

本文用原子集团模型和嵌入原子方法,计算研究了H在Ni(100),(110)和(111)表面上的扩散特性,其扩散激活能分别是0.152eV;0.343eV和0.142eV。Ni(100)面上的吸附Ni原子和Ni原子空位,分别是在其表面上扩散的H原子的一种陷阱和位垒;Ni(100)面上的台阶,将使通过此台阶的H原子的扩散势垒增高,激活能增大,且引起扩散的各向异性。     

氧原子在Zr(0001)表面附近的扩散

在密度泛函理论计算的基础上,利用微动弹性带（nudged elastic band）方法研究了氧原子在Zr（0001）表面附近的扩散.首先计算了氧原子从稳定的表面面心立方（SFCC）位置向表面六角密排位置的扩散激活能（0.77 eV）;然后计算了氧原子从稳定的SFCC位置扩散到表面下第1层与第2层之间的八面体间隙位置,再继续向表面下第2层与第3层之间的八面体间隙位置扩散的激活能,在此过程中氧原子需克服两个能垒,其激活能分别为2.14和2.57 eV.结果表明,氧原子在Zr（0001）表面上方的扩散比较容易,而氧原子向Zr（0001）表面下的扩散相对较难. 关键词： Zr（0001）表面 微动弹性带 氧的扩散     

氧原子在α钛晶体中扩散的第一性原理研究

在材料领域杂质原子的迁移是一个基础而永恒的主题.采用基于密度泛函理论的第一性原理方法,研究了氧原子在α钛(α-Ti)晶体中的间隙占位情况,并计算了氧原子稳定占位点间隙能、电子态密度、电荷差分密度及其邻近钛原子的位移情况.采用基于过渡态搜索理论的CI-NEB(climbing image nudged elastic band)方法预测了稳定态氧原子在α-Ti晶体中的扩散路径、扩散势垒及相应的跳转频率,并由此推算出氧原子在不同位点之间跳转的扩散系数.研究结果表明,间隙氧原子在六角密排钛晶体结构中共有七种占位,但仅存在三个可稳定占据的间隙位点:八面体中心位点、六面体中心位点及0.28 nm钛—钛键中心位点.各稳定间隙位点之间的扩散具有不对称性,因此可确定三种稳定间隙氧原子位点间存在七条独立扩散路径.获取计算不同路径扩散系数所需要的微观参数,包括扩散势垒、扩散长度、不同扩散路径上鞍点氧原子的跳转频率,最终预测了不同间隙位点之间氧原子的扩散系数值,其中八面体中心扩散到邻近键位的扩散系数与实验值相符合.通过对间隙氧原子扩散行为的深入了解,希望能对控制钛合金中氧的扩散、提高钛金属中氧的含量及相关研究提供基础理论支持.     

γ-Fe中氢扩散行为的第一性原理研究

不锈钢中氢脆问题一直是研究者们关注热点,然而至今为止,对于钢中合金元素及空位与H原子之间的作用机理依然不清晰.采用第一性原理方法研究了H原子在不同体系下γ-Fe(Fe₈H、Fe₇Cr/MoH、Fe₇H)的扩散激活能、扩散系数以及扩散过渡态,对比了H原子在不同体系γ-Fe中的扩散难易程度,并从电子结构层次解释其相互作用.研究结果表明,空位的存在会改变H原子在γ-Fe中的扩散路径.在含空位的晶胞中H原子稳定存在于空位附近的近四面体间隙中,并沿空位附近的四面体间隙或八面体到四面体间隙路径扩散. γ-Fe中空位对H原子的影响是局域性的,一方面是捕获H原子的陷阱;另一方面降低了H原子的扩散激活能,促进H原子的扩散.而Cr/Mo的掺杂会降低空位对H原子的束缚,也会抑制H原子的扩散.     

KDP晶体本征中性点缺陷的第一性研究

 用第一性原理研究了KH2PO4(KDP)晶体中性本征点缺陷的形成能并计算了常温下点缺陷的浓度。计算得到中性填隙氢原子的形成能为2.05 eV，进而得到298 K下的浓度约为1.21×10^-17 mol/L。由于填隙氢原子在带隙中形成缺陷能级，并使能隙降低了2.6 eV, 因此消除填隙氢原子有利于提高晶体在355 nm附近的激光损伤阈值。计算得到的氧间隙、氧空位、钾空位和氢空位的形成能分别为0.60、5.25、6.50 和6.58 eV，常温下它们在晶体中也以较高的浓度存在。钾空位使晶胞体积增大约3.2%，并可能提高晶体电导率，从而降低光损伤阈值。P取代K的反位结构缺陷形成能尽管较低(4.1 eV), 但由于晶体生长溶液中P是以PO4四面体的形式存在，故此点缺陷的存在几率很小。     

本征缺陷对β-Ga2O3光催化性质影响的第一性原理研究

运用第一性原理杂化泛函研究了本征缺陷(O空位和Ga空位)对于β-Ga₂O₃的几何结构和电子性质的影响.计算结构表明:杂化泛函B3LPY能很好的描述β-Ga₂O₃的几何结构和电子结构,能与实验符合.含O缺陷的形成能在富氧和贫氧下分别为4.04和0.92 eV,优于含Ga缺陷的体系.空位缺陷的出现对于理想Ga₂O₃的晶格参数影响不显著,只是在O空位体系中,空位附近Ga-O键长有0.1?变化.含空位缺陷的体系的禁带中都有缺陷能级的出现,含Ga和O空位缺陷的Ga₂O₃的光跃迁能分别为1.93 eV(β自旋)和2.92 eV,有很明显的光吸收的拓展,从理论上解释了Ga₂O₃作为光催化材料的潜在应用.     

氧空位对ZnO基(110)二维膜材料电子结构的影响研究

在密度泛函理论方法的基础上,系统研究了本征氧化锌和氧空位氧化锌的(110)二维膜材料的形成和电子结构性质.计算分析结果表明,ZnO的本征(110)二维膜比氧空位的(110)二维膜稳定性高,ZnO的(110)二维膜有失去氧的倾向.本征ZnO的(110)膜为直接带隙型材料,带隙宽度为2.3 eV,氧空位(110)膜为间接带隙型材料,带隙宽度为1.877 eV.氧空位的(110)膜导带向下移动,并且导带中的能级简并化.氧空位(110)膜材料的导带底能级有2个能谷,分别位于1.877 eV和1.88 eV,这些位置的能级有效质量比本征膜大幅度增大,这些位置的电子速度普遍较低. ZnO的(110)膜产生氧空位之后,Zn的s电子参与形成其价带顶能级.氧空位(110)膜材料中Zn-O键的混合型结合倾向增大.     

缺陷TiO2中铁磁性的第一性原理计算

计算钛空位（V_Ti）和氧空位（V_O）共存情况下未掺杂金红石TiO₂的铁磁性.发现V_O可以产生局域磁矩,由它引起的自旋极化比V_Ti引起的更加局域,导致V_O之间的铁磁耦合作用弱于V_Ti之间的铁磁耦合作用.V_Ti之间的铁磁耦合在引入V_O之后进一步加强.V_O引入的电子调制两个分离的V_Ti之间的长程铁磁耦合.加入V_Ti之后,两个V_O的磁矩猝灭,当V_O的数量多于V_Ti的数量二倍时,V_O会对磁矩有贡献.结果与实验发现的V_O可以提高铁磁有序,并且总的磁矩会随着V_O数量的增多而增加的结果符合很好.     

Ce和O空位共掺杂TiO_2的电子结构与光学性质

采用基于密度泛函理论加U的计算方法,研究了Ce和O空位单(共)掺杂锐钛矿相TiO_2的电子结构和光吸收性质.计算结果表明,Ce和O空位共掺杂TiO_2的带隙中出现了杂质能级,且带隙窄化为2.67 eV,明显比纯TiO_2和Ce,O空位单掺杂TiO_2的要小,因而可提高TiO_2对可见光的响应能力,使TiO_2的光吸收范围增加.光吸收谱显示,掺杂后TiO_2的光吸收边发生了显著红移;在400.0—677.1 nm的可见光区,共掺杂体系的光吸收强度显著高于纯TiO_2和Ce单掺杂TiO_2,而略低于O空位单掺杂TiO_2.此外,Ce掺杂TiO_2中引入O空位后,TiO_2的导带边从-0.27 eV变化为-0.32 eV,这表明TiO_2的导带边的还原能力得到了加强.计算结果为Ce和O空位共掺杂TiO_2在可见光光解水方面的进一步研究提供了有力的理论依据.     

重氧空位对金红石型和锐钛矿型TiO2导电性能影响的模拟计算

基于密度泛函理论框架下的第一性原理平面波超软赝势方法,构建了未掺杂与相同重氧空位金红石型和锐钛矿型TiO_1.9375超胞模型,分别对模型进行了几何结构优化、能带结构分布和态密度分布的计算. 结果表明,氧空位后金红石型和锐钛矿型TiO₂体系体积均变大,同时,锐钛矿型TiO_1.9375超胞的稳定性、迁移率以及电导率均高于金红石型TiO_1.9375超胞. 计算结果和实验结果相一致. 关键词： 重氧空位 2')" href="#">金红石型和锐钛矿型TiO₂ 导电性能 第一性原理     

Dissociation of liquid water on defective rutile TiO2 (110) surfaces using ab initio molecular dynamics simulations

In order to obtain a comprehensive understanding of both thermodynamics and kinetics of water dissociation on TiO₂, the reactions between liquid water and perfect and defective rutile TiO₂ (110) surfaces were investigated using ab initio molecular dynamics simulations. The results showed that the free-energy barrier (~4.4 kcal/mol) is too high for a spontaneous dissociation of water on the perfect rutile (110) surface at a low temperature. The most stable oxygen vacancy (V_o1) on the rutile (110) surface cannot promote the dissociation of water, while other unstable oxygen vacancies can significantly enhance the water dissociation rate. This is opposite to the general understanding that V_o1 defects are active sites for water dissociation. Furthermore, we reveal that water dissociation is an exothermic reaction, which demonstrates that the dissociated state of the adsorbed water is thermodynamically favorable for both perfect and defective rutile (110) surfaces. The dissociation adsorption of water can also increase the hydrophilicity of TiO₂.     

First-principles study of the structural,electronic, and magnetic properties of double perovskite Sr_2FeReO_6 containing various imperfections

The structural, electronic, and magnetic properties of double perovskite Sr_2FeReO_6 containing eight different imperfections of FeReor ReFeantisites, Fe1–Re1 or Fe1–Re4 interchanges, V_(Fe), V_(Re), VOor V_(Sr) vacancies have been studied by using the first-principles projector augmented wave(PAW) within generalized gradient approximation as well as taking into account the on-site Coulomb repulsive interaction(GGA+U). No obvious structural changes are observed for the imperfect Sr_2FeReO_6 containing FeReor ReFeantisites, Fe1–Re1 or Fe1–Re4 interchanges, or VSrvacancy defects. However, the six(eight) nearest oxygen neighbors of the vacancy move away from(close to) VFeor V_(Re)(VO) vacancies. The half-metallic(HM) character is maintained for the imperfect Sr_2FeReO_6 containing FeReor ReFeantisites, Fe1–Re4 interchange, V_(Fe),VO or V_(Sr) vacancies, while it vanishes when the Fe1–Re1 interchange or VRevacancy is presented. So the Fe1–Re1 interchange and the VRevacancy defects should be avoided to preserve the HM character of Sr_2FeReO_6 and thus usage in spintronic devices. In the FeReor ReFeantisites, Fe1–Re1 or Fe1–Re4 interchanges cases, the spin moments of the Fe(Re)cations situated on Re(Fe) antisites are in an antiferromagnetic coupling with those of the Fe(Re) cations on the regular sites. In the V_(Fe), V_(Re), VO, or V_(Sr) vacancies cases, a ferromagnetic coupling is obtained within each cation sublattice,while the two cation sublattices are coupled antiferromagnetically. The total magnetic moments μtot(μB/f.u.) of the imperfect Sr_2FeReO_6 containing eight different defects decrease in the sequence of VSrvacancy(3.50), VRevacancy(3.43),FeReantisite(2.74), VOvacancy(2.64), VFevacancy(2.51), ReFeantisite(2.29), Fe1–Re4 interchange(1.96), Fe1–Re1interchange(1.87), and the mechanisms of the saturation magnetization reduction have been analyzed.     

The theoretical study of the cationic conductivity of AgBr

AgCl and AgBr are a special type of superionic conductor, whose superionic phase transition does not accompany any first-order structural phase transition. In the paper, the ionic conductivity of AgBr is investigated by the first principles calculations with VASP code. The calculated results show that the isolated charged interstitial or vacancy is always more stable than the neutral one whether the system is doped or not; the interstitial hops along <001> direction, and the potential barrier is 0.29 eV; the vacancy hop mainly along <111> direction, and the barrier is 0.16 eV; the migration barrier of vacancy is obviously lower than that of interstitial, and then the ionic conductivity is mainly due to the diffusions of vacancies.     

C掺杂金红石相TiO2的电子结构和光学性质的第一性原理研究

运用第一性原理的局域密度近似+U(0 ≤U≤9 eV)方法研究了本征金红石相TiO₂在不同U值(对Ti-3d电子)下的禁带宽度、晶体结构以及不同比例C元素掺杂的金红石相TiO₂的电子结构和光学性质, 研究表明, TiO₂的禁带宽度和晶格常数随着U值的增加而增大. 综合考虑取U=3 eV并对其计算结果进行修正. 对于掺杂体系, 发现C 元素的掺杂在金红石相TiO₂中引入杂质能级, 杂质能级主要由O-2p轨道和C-2p轨道耦合形成, 杂质能级的引入可以增加TiO₂对可见光的响应, 从而使TiO₂的吸收范围增大. C原子掺杂最佳比例为8.3%, 此时光学吸收边的红移程度最明显, 可增大光吸收效率, 从而提高了TiO₂光催化效率.     

高氧空位浓度对金红石TiO2导电性能影响的第一性原理研究

采用基于密度泛函理论的平面波超软赝势方法研究了 纯的和不同高氧空位浓度金红石型TiO_2-x (x=0, 0.083, 0.125, 0.167, 0.25)超胞的能带结构分布、态密度分布.同时, 采用局域密度近似+U方法调准了带隙.结果表明, 高氧空位浓度越高, 金红石型TiO₂的最小带隙越变窄、电子有效质量越减小, 自由电子浓度越高, 电子迁移率越低、电导率越低.计算结果与实验结果的变化趋势相符合. 关键词： 高氧空位 2')" href="#">金红石型TiO₂ 电导率 第一性原理     

DFT modeling of the hydrolysis of isocyanic acid over the TiO2 anatase (1 0 1) surface: Adsorption of HNCO species

The nature of the interaction of isocyanic acid (HNCO) with the active centers at the ideal anatase TiO₂ (1 0 1) surface were studied using ab initio density functional theory (DFT) method with a cluster model. Two types of adsorption of isocyanic acid are found to be likely at (1 0 1) surface – dissociative and molecular adsorption. Only molecular adsorption of HNCO leads to the direct weakening and further splitting of the NC bond, which is a necessary step for the hydrolysis of isocyanic acid. During molecular adsorption of HNCO, an energetically stable intermediate surface complex is created with an adsorption energy of −1.33 eV, in which the HNCO skeleton is changing due to new strong bonds between C–O_s and N–Ti_s. Based on the existence of this intermediate complex a probable reaction pathway for the hydrolysis of HNCO over the ideal anatase (1 0 1) surface was developed. A surface oxygen vacancy was formed after the decomposition of the intermediate complex and CO₂ desorption. Afterwards, water adsorbs at the oxygen vacancy site and NH₃ is successively formed. The HNCO hydrolysis over TiO₂ was found to be energetically favorable with global energy gain of about −2.08 eV.