Prediction of the Frontier Electronic States in a Finite Single-wall Carbon Nanotube

A theoretical model is summarized into the shorter vector principle. It is used to predict the topological structure of wave function and the oscillation rule of energy gap in various types of finite carbon nanotubes (CNTs). The theoretical model indicates that the characteristics of the electronic states only depend on the nanotube size and its symmetry along the shorter vector direction. In this direction, the wave functions of the original 3m (or 3m/2) periodicity are also suitable for armchair, chiral and zigzag finite CNTs with the C2 (Cs), C1 and Cn point groups, respectively. Energy gaps present the oscillation with 3m (or 3m/2) or odd-even n. The first principle calculations for some prototype systems are performed. The results are consistent with the theoretical model.     

A First-principles Study on the Gas Sensitivity of Metal-loaded Graphene with an Atomic Vacancy to O_2

In this work, adsorption energies, geometrical and electronic structures for adsorption systems of O_2 at metal-loaded graphene(M-Gra) and metal-loaded defective graphene(M-D-Gra)(M = Ni, Pd, Pt and Al) surfaces are studied using a GGA-PW91 method. Calculated results show that loaded M make the interaction between O_2 and the graphene surface change from physical to chemical adsorptions, band gaps of M-Gra systems after the O_2 adsorption change, and the Ni-loaded Gra has the highest sensitivity to O_2. For O_2-M-D-Gra systems, interactions between O_2 and the M-D-Gra surfaces are chemical, similar to the O_2-M-Gra systems, and loaded Pt and Al have the strongest effect on the sensitivity of D-Gra to O_2. The M loads at the perfect Gra and D-Gra surfaces make the interactions between O_2 and the surfaces have obvious charge transfer. This work would provide a valuable guidance on the gas sensitivity study of graphene to O_2.     

CaO或BaO与Sm2O3共掺杂CeO2体系电子结构和氧离子迁移的DFT+U研究

使用GGA+U方法研究了Ca O或Ba O与Sm2O3共掺杂Ce O2体系几何和电子结构及氧离子迁移。计算结果表明,Ba和Sm均靠近氧空位时Ba Sm Ce30O63体系最稳定;Sm靠近,Ca远离氧空位时Ca Sm Ce30O63体系最稳定。Ba Sm Ce30O63和Ca Sm Ce30O63体系中均不存在Ce4+变价。对Ca Sm Ce30O63体系氧离子迁移的研究发现,当氧离子迁移到空位时,迁移能大小顺序为Em(3→V)Em(1→V)Em(4→V)Em(2→V),这一规律源于氧离子与低价掺杂离子产生负电势之间的排斥作用;对Ba Sm Ce30O63体系氧离子迁移的研究发现,当空位迁移到周围氧离子时,迁移能大小顺序为Em(V→3)Em(V→5)Em(V→1),这一规律源于氧空位产生的正电势与低价掺杂离子产生的负电势之间的吸引作用。此外,Ca Sm Ce30O63体系最小迁移能小于Sm Ce31O63体系,证实了Ce O2-Sm2O3-Ca O体系离子电导率大于Ce O2-Sm2O3体系的实验结果。     

Effects of Doping and Oxygen Vacancy Concentrations on Oxygen Ion Migration in Sm_xCe_(1-x)O_(2-δ): a DFT + U Study

Influence of doping and oxygen vacancy concentrations on oxygen ion or oxygen vacancy(V) migration energies of Sm_xCe_(1-x)O_(2-δ)(x = 0.0625, 0.125, 0.25 and δ = 0.0625, 0.125) systems using a GGA+U method are studied. Calculated results show that advantage migration types change from V?O~(2-) to O~(2-) ?V as x and δ increase. For V?O~(2-) migrations of the Sm_(0.0625)Ce_(0.9375)O_(1.9375) and Sm_(0.125)Ce_(0.875)O_(1.9375) systems, electrostatic attractions between Sm~(3+) and V, defect associations between Ce~(3+) and V, and steric hindrances of Sm~(3+) affect the migration energies. For O~(2-) ?V migrations of the Sm+(0.125)Ce_(0.875)O_(1.875) and Sm_(0.25)Ce_(0.75)O_(1.875) systems, migration energies of O~(~(2-) ) are affected by electrostatic repulsions between Sm~(3+) and O~(2-) and defect associations between Ce~(3+) and V. Increases of the oxygen vacancy and Sm~(3+) doping concentrations benefit the oxygen ion and vacancy migrations, respectively.     

Li在石墨烯、BC7及C7N表面吸附与迁移的第一性原理研究

基于密度泛函理论的第一性原理方法,本文系统研究了Li在本征石墨烯及BC7、C7N表面的吸附和迁移行为。与本征石墨烯相比,硼含量为12.5at%时提高了Li的吸附能,而氮含量为12.5at%时减弱了Li的吸附能,这归因于掺杂物种具有不同的电子结构。通过NEB方法计算了Li在本征石墨烯、BC7、C7N表面的迁移。结果表明,相比于本征石墨烯,硼含量为12.5at%的石墨烯减弱了Li的扩散,而氮含量为12.5at%的石墨烯促进了Li的扩散,有助于提高石墨烯负极材料的充放电性能。     

CaO或BaO与Sm2O3共掺杂CeO2体系电子结构和氧离子迁移的DFT+U研究

使用GGA+U方法研究了CaO或BaO与Sm₂O₃共掺杂CeO₂体系几何和电子结构及氧离子迁移。计算结果表明,Ba和Sm均靠近氧空位时BaSmCe₃₀O₆₃体系最稳定;Sm靠近,Ca远离氧空位时CaSmCe₃₀O₆₃体系最稳定。BaSmCe₃₀O₆₃和CaSmCe₃₀O₆₃体系中均不存在Ce⁴⁺变价。对CaSmCe₃₀O₆₃体系氧离子迁移的研究发现,当氧离子迁移到空位时,迁移能大小顺序为E_m(3→V)< E_m(1→V)< E_m(4→V)< E_m(2→V),这一规律源于氧离子与低价掺杂离子产生负电势之间的排斥作用;对BaSmCe₃₀O₆₃体系氧离子迁移的研究发现,当空位迁移到周围氧离子时,迁移能大小顺序为E_m(V→3)< E_m(V→5)< E_m(V→1),这一规律源于氧空位产生的正电势与低价掺杂离子产生的负电势之间的吸引作用。此外,CaSmCe₃₀O₆₃体系最小迁移能小于SmCe₃₁O₆₃体系,证实了CeO₂-Sm₂O₃-CaO体系离子电导率大于CeO₂-Sm₂O₃体系的实验结果。     

有限长锯齿型碳纳米管的电子结构与管径效应

在B3LYP／6—31G／／PM3水平上对一系列有限长锯齿型碳纳米管(n，0)(n=6-11)的构型和电子结构进行了研究．结果表明，最高占据轨道(HOMO)与最低空轨道(LUMO)间的能隙(Eg)随着管径的增大出现随奇偶n值的振荡变化，随着管长的增加呈单调减小的趋势；前线轨道波函数的成键结构随管径的变化而变化，但并不随管长的变化而改变，HOMO的成键性质与几何结构之间存在对应关系．     

Al掺杂的锂离子电池层状正极材料Li(Li0.17Ni0.17Al0.04Fe0.13Mn0.49)O2结构稳定性及氧离子氧化的理论研究

锂离子电池(LIB)正极材料比容量及结构稳定性的提高是提升电池整体性能的重要因素. 本工作选取层状无钴正极材料Li(Li_0.17Ni_0.17Al_0.04Fe_0.13Mn_0.49)O₂ (LNAFMO)为研究对象, 使用GGA (generalized gradient approximation)+U (Hubbard U value)方法研究了体系在充电时几何和电子结构变化、氧释放焓、脱锂形成能和脱锂电压. 研究结果表明, 充电时LNAFMO体系首先Ni氧化, 然后Fe氧化, 最后O氧化. 与未掺杂Al的Li(Li_0.17Ni_0.17Fe_0.17Mn_0.49)O₂ (LNFMO)体系不同的是, 除具有线性Li-O-Li和Fe-O-Li构型的氧离子更容易给出电子外, 具有线性Al-O-Li构型的氧离子也参与电荷补偿, 并且氧离子具有很强的活性, 这将避免参与氧化的氧离子过分集中, 有利于结构的稳定; Al的掺杂能进一步抑制氧的释放, 这将提升体系的结构稳定性和电池循环性能. 该研究为设计一种低经济成本、循环性良好、高能量密度的锂离子电池正极材料奠定了坚实的理论依据.     

Transitional Area of Ce~(4+) to Ce~(3+) in Sm_xCa_yCe_(1-x-y)O_(2-δ) with Various Doping and Oxygen Vacancy Concentrations: A GGA + U Study

In this work,we perform DFT+U periodic calculations to study geometrical and electronic structures and oxygen vacancy formation energies of Sm_xCa_yCe_(1-x-y)O_(2-δ)systems(x=0.0312,0.0625,0.125 and 0.250;y=0.0312,0.0625,0.125 and 0.250;δ=0.0312,0.0625,0.125,0.250 and 0.50)with different oxygen vacancy and doping concentrations.The calculated results show that the V_1-Sm~(3+)-V_2 structures where there is a position relationship of the face diagonal between V_1 and V_2 both nearest to Sm~(3+)have the lowest energy configurations.The study on electronic structures of the Sm_xCa_yCe_(1-x-y)O_(2-δ)systems finds that excess electrons arise from oxygen vacancies and are localized on f-level traps of their neighbor Ce,and Ca~(2+)and Sm~(3+)co-doping effectively restrains the reduction of Ce~(4+).In order to avoid the existence of Ce~(3+),x and y must be both larger than 0.0625 asδ=0.125 orδmust be smaller than 0.125 as x=y=0.0625.The Ce~(3+)/Ce~(4+)change ratio k has an obvious monotonous increase with increasing the vacancy oxygen concentration.The introduction of Sm~(3+)decreases k.In addition,the doped Sm~(3+)can restrain the reduction of Ce~(4+)when the V_1-Sm~(3+)-V_2 structure with a face diagonal position relationship in lower reduced atmosphere exists.It need be pointed out that the Sm_(0.25)Ce_(0.75)O_(1.5) system should be thought of as a Sm-doped Ce_2O_3 one.     

基于曲率和电子结构的掺杂C50和C70富勒烯的稳定性研究

使用密度泛函理论(DFT)-B3LYP/6-31G^*方法研究了B、N、Si、P和Co在C₅₀和C₇₀中的掺杂能和电子结构, 并基于曲率理论和电子结构探讨了掺杂富勒烯的结构稳定性. 计算结果表明, 掺杂能随着原子曲率的增大而减小, 随着掺杂物种原子半径的增大而增大, B、N、P和Co的掺杂有利于C₅₀结构的稳定, 而B和N的掺杂不利于C₇₀结构的稳定; 除了用于反映原子活性的曲率主要决定掺杂反应性, 各不等价碳原子在C₅₀和C₇₀的最高占据分子轨道(HOMO)中所占成分对掺杂能的影响也很大, 且其成分越大越有利于掺杂. 此外, 掺杂原子得失电子情况与其电负性有关. 本工作将为富勒烯结构稳定性的研究提供理论依据.