铑原子基态的理论研究

在有心力场近似和组态相互作用理论框架下,通过对电子波函数、各个壳层上电子的束缚能、平均轨道半径、总束缚能、基组态时的激发能、电离能的分析和计算,研究了Lr原子的可能基组态及其基组态时的原子态.研究结果表明:基组态为5f147s27p,基态时的原子态为2P1/2.     

第一性原理对SinMg(n=1-12)团簇结构、稳定性与电子性质的研究

运用密度泛函理论(DFT)的杂化密度泛函B3LYP方法,在6-311G基组水平上对 团簇进行了构型优化、频率分析与电子性质计算.同时讨论了团簇的平均结合能、能级间隙、二阶能量差分、自然电子布居、极化率.研究结果表明： 团簇的基态绝大多数为立体结构. 时,体系的基态为自旋三重度, 时,则为单重态.镁原子的掺入使得主团簇的电子性质发生了明显的变化,掺杂使体系的平均结合能降低,能隙减小,化学硬度减小,电子亲和能增大.电子总是从 原子向 原子转移.团簇中原子之间的成键相互作用随n的增大 而增强,团簇的电子结构随n的增大而趋于紧凑.     

类Li和类Be等电子序列离子基组态能量的Z相关修正

在相对论多体微扰理论和屏蔽理论的基础上,本文提出了一种计算等电子序列离子基组态能量的新方法,通过引入一个与核电荷数Z相关的能量修正函数γ(Z)来考虑由于忽略能量的高阶项对原子体系基组态能量的影响。在对类Li(Z=3～50)和类Be(Z=4～50)等电子序列离子的基组态能量所进行的理论计算研究结果表明,Z相关能量修正对于原子体系基组态能量的准确计算是有效的。     

第一性原理对Si_nMg(n=1～12)团簇结构、稳定性与电子性质的研究

运用密度泛函理论(DFT)的杂化密度泛函B3LYP方法,在6-311G基组水平上对SinMg(n=1～12)团簇进行了构型优化、频率分析与电子性质计算.同时讨论了团簇的平均结合能、能级间隙、二阶能量差分、自然电子布居、极化率.研究结果表明:SinMg(n=1～12)团簇的基态绝大多数为立体结构.n=1时,体系的基态为自旋三重度,n≥2时,则为单重态.镁原子的掺入使得主团簇的电子性质发生了明显的变化,掺杂使体系的平均结合能降低,能隙减小,化学硬度减小,电子亲和能增大.电子总是从Mg原子向Si原子转移.团簇中原子之间的成键相互作用随n的增大而增强,团簇的电子结构随n的增大而趋于紧凑.     

TiAl电子态结构的ab initio计算

应用完全活动基自洽场方法,结合N电子价态微扰近似(NEVPT2),对TiAl金属二聚体的基态和若干最低电子激发态的势能曲线进行了计算.完全活动空间由Al的3个价电子(3s23p1)轨道和Ti的4个价电子(3d24s2)轨道构成,计算基组选用Karlsruhe group的价分裂全电子基组def2-n ZVPP(n=T, Q).在确认TiAl的基态为四重态的基础上,在核间距R=0.200—0.500 nm范围内,扫描获得了TiAl基态和最低二个激发态的完整势能曲线,并对电子态进行了标识,发现在0.255 nm附近存在电子态结构的"突变".在R0.255 nm区域,基态和两个激发态分别为X~4Δ, A~4Π和B~4Γ;在R 0.255 nm区域,基态仍为X~4Δ,但两个激发态变为A'~4Φ和B'~4Π,且存在激发态简并解除的现象.基于NEVPT2修正后的势能曲线,获得了TiAl电子态的平衡核间距、束缚能、激发能、跃迁偶极矩等特征参数,并解释了实验上观测不到TiAl电子跃迁光谱的原因.电子激发态存在"突变"的结构特征,可为分析理解TiAl合金在室温下的脆性问题提供参考.     

FeVO_4电子结构的第一性原理研究

采用基于密度泛函理论的第一性原理方法研究了三斜结构FeVO_4的结构,基态的能带结构、总态密度和分波态密度.将FeVO_4非共线的螺旋磁结构简化为六种不同的反铁磁结构,通过比较不同自旋构型的总能确定了基态磁结构.能带计算和总态密度结果均显示FeVO_4是能隙为2.19 e V的半导体,与实验结果相符.考虑Fe原子的在位库仑能,FeVO_4的能带结构和态密度都发生变化,说明FeVO_4晶体是一个典型的强关联电子体系.     

弱耦合多原子半无限晶体中磁极化子的激发能量

近年来国内外对多原子极性晶体中磁极化子性质的研究十分活跃,Zorkani等采用变分法计算了束缚磁极化子的基态能量,Kandemir等采用束缚朗道态讨论了二维大磁极化子的基态和第一激发态能量,国内一些学者采用微扰法和新颖算符法讨论了多原子极性晶体中表面和体磁极化子的性质。采用线性组合算符和幺正变换,研究磁场中多原子半无限极性晶体中电子和光学声子弱耦合相互作用所产生的极化子的第一激发态能量及平均声子数。结果表明:当电子无限接近晶体表面时,磁极化子的基态能量仅为Landau能量;第一激发态能量为Landau基态能量的2倍;平均声子数等于各支与电子耦合的体光学声子数和表面光学声子数之和。而当电子处于晶体深处时,磁极化子的基态能量却为Landau基态能量与各支体光学声子以及表面光学声子分别耦合的能量之和;第一激发态能量仍为Landau基态能量的2倍;平均声子数等于各支与电子耦合的体光学声子数和与所处深度有关的各支体光学声子数之和,而与各支表面光学声子无关。     

导电高聚物中电子转移积分计算

在“紧束缚近似”下，假定聚乙炔中每个碳原子都处于基态，并取基态原子波函数为类氢原子的２Ｐ_z态，将其线性组合后作为π电子的波函数。在此基础上，研究了多中心积分问题，给出了转移积分的解析表达式。     

半导体束缚激子基态能的变尺度法

提出了计算体系基态能的变尺度法，用该算法计算了电子和空穴有效质 量比值不同时，离子化施主束缚激子（D+，X）的基态能. 在求解体系基态能上与传统的变分法相比有很大的优势，尤其适合复杂体系基态能的计算. 关键词： 束缚激子 氦原子 基态能 变尺度方法     

钒氢分子及离子的势能函数与垂直电离势

为了搞清储氢材料的机理,需了解VHn(n=0、 1、 2)分子及离子体系势能函数和稳定性的信息,本工作用原子分子反应静力学原理推导出了VHn(n=0、 1、 2)的基态电子状态及其离解极限.对H原子采用6-311 G**基组,对V原子采用SVP全电子基组,用B3PW91方法计算了它们的平衡几何、离解能,在此基础上分别计算了VH,VH 1的Murrell-Sorbie解析势能函数和基态VH 2的解析势能函数及其对应的力常数、光谱参数和垂直电离势.计算表明VH 离子的2Σ 和4Δ以及VH2 离子的1Σ 均具有对应于离子稳定平衡结构的极小点,说明它们可稳定存在.而VH (6Σ )、基态的VH2 (3Φ)和VH2 (5Σ )离子的离解能太小,应是不稳定的.     

(CrO4)络离子中Cr-O距离的研究

通过MS-X_α方法的计算详细地讨论当Cr—O距离变化时(CrO₄)络离子的电子结构和能级分布。给出铬离子三种不同价态(Cr²⁺,Cr³⁺,Cr⁴⁺)的单电子轨道能量、电荷分布、基态电子组态、低激发态的光学跃迁,以及能级示意图。当配位体与中心离子的距离R≤2?时,用晶场理论得出的结果不能令人满意。这时必须考虑配位体与中心离子距离的影响,以及中心离子(对于过渡族金属离子而言)的4s或4p原子轨道的作用。 关键词：     

Visible spectra of heavy ions with an open 4f shell

We present visible to near-infrared spectra of highly charged Yb (the atomic number 70) and W (74) obtained with a compact electron beam ion trap. By observing the dependence on the electron beam energy, the charge state that should be assigned to the observed lines is determined. For In-like Yb²¹⁺ and W²⁵⁺ and Sn-like W²⁴⁺, the experimental spectra are compared with theoretical calculations done by the CI+all-order method. In each spectrum, the most prominent line is identified as the magnetic dipole transition from the first excited fine structure level to the ground level in the ground electronic configuration, 4f³ for In-like ions and 4f⁴ for Sn-like ions.     

Magnetic ground state and electronic structure of CeRu(2)Al(10)

We present a combined theoretical and experimental study of the electronic structure for CeRu(2)Al(10) based on ab initio band structure calculations and x-ray photoemission spectroscopy (XPS) data. Our calculations were performed for the base unit cell and for the hypothetical unit cell which enables antiferromagnetic ordering. The stability of the magnetic phase was investigated within fixed spin moment calculations. When additional 4f correlations are not included in the LSDA C U approach, CeRu(2)Al(10) exhibits an unstable magnetic configuration with the difference in total energy per unit cell between the weakly magnetic state and the non-magnetic one of the order ~0.3 meV. We found that Coulomb correlations among 4f electrons, when they are included in the LSDA C U approach, stabilize the magnetic structure. In the weakly correlated system (small U) an antiferromagnetic (AFM) ground state with the lowest total energy is preferred. The situation is, however, the opposite when the 4f correlations are strong. In this case the ferromagnetic (FM) ground state is preferred. By comparing our calculations with the experimental data we conclude that the 4f correlations in CeRu(2)Al(10) are weak. We also carried out a structural relaxation of atomic positions within the Cmcm unit cell and we found that the Al atoms exhibit noticeable displacement from their positions known from x-ray diffraction (XRD) analysis.     

Fragmentation of polyatomic ions produced by electron-loss collisions of butane and isobutane molecules with ions of kiloelectronvolt energy

Fragmentation accompanying the loss of electrons by butane and isobutane (C₄H₁₀) molecules in collisions with energy H⁺, He²⁺, and Ar⁶⁺ ions of kiloelectronvolt energies is studied. The electron density functional technique is applied to C _n H_2n+2 alkane molecules and their respective C _n H _2n+2 ⁺ ions to carry out quantum-chemical calculations of the atomic spacing, electron total energy for the initial configuration of the ionizing molecules and ions in the ground state, and atomic bond breaking energy necessary to produce different ion fragments. The fragmentation energy is correlated with the fragmentation probability. It is shown that the relative cross sections of ion fragmentation depend primarily on the related energy consumption. However, the process cross section is also strongly affected by the initial configuration of C₄H₁₀ isomer molecules, as well as by the amount of dangling and arising atomic bonds involved in the formation of each ion fragment.     

Three-spin interactions in optical lattices and criticality in cluster Hamiltonians

We demonstrate that in a triangular configuration of an optical lattice of two atomic species a variety of novel spin-1/2 Hamiltonians can be generated. They include effective three-spin interactions resulting from the possibility of atoms tunneling along two different paths. This motivates the study of ground state properties of various three-spin Hamiltonians in terms of their two-point and n-point correlations as well as the localizable entanglement. We present a Hamiltonian with a finite energy gap above its unique ground state for which the localizable entanglement length diverges for a wide interval of applied external fields, while at the same time the classical correlation length remains finite.     

Arbitrary quantum superposition state for three-level system using oscillating dark states

An method for adiabatic population transfer and the preparation of an arbitrary quantum superposition state using the oscillating dark states (ODS) in atomic system is presented. Quantum state of a three-level Λ configuration atomic system finally evolves into the same time-dependent state, and oscillates periodically between two ground levels under evolving adiabatic conditions when two pairs of classical detuning laser fields drive the system into the ODS forcedly, whatever the initial states of the system are. The decoherence of the ODS evolution is greatly suppressed and the oscillation is very stable, therefore adiabatic population transfer and the preparation of an arbitrary quantum superposition state of atomic system can be completed accurately and conveniently.     

HNO分子基态的结构与解析势能函数研究

应用群论及原子分子反应静力学的方法, 导出了HNO分子基态电子态和合理的离解极限.利用优选出的密度泛函理论B3LYP方法结合6-311G **优化计算了HNO分子基态的平衡结构和谐振频率.计算结果表明基态HNO分子稳定态为C_S构型,电子组态为X¹A',平衡核间距分别为R_H-N=0.1065 nm,R_N-O=0.1200 nm,键角∠H-N-O=108.60°,离解能D_e=15.379 eV.基态简正振动频率分别为:弯曲振动频率ν₁=1575.6351 cm^-1,对称伸缩振动频率ν₂=1673.2890 cm^-1,反对称伸缩振动频率ν₃=2837.7856 cm^-1.在此基础上,应用多体项展式理论导出了基态HNO分子的全空间解析势能函数,该势能函数等值势能图准确再现了HNO分子平衡结构和离解能. 关键词： 势能函数 光谱常数 密度泛函方法     

中低温等离子体原子能量的分波法计算

在改进的平均原子模型的基础上，在中心场近似下用分波法处理自由电子密度分布函数，提高了电子波函数、电子占据数等原子参数的计算精度.通过使用分波法准确计算电子间各部分的相互作用能，使得原子能量的计算结果更加准确，零温基态能的计算结果与Hartree-Fock理论给出的结果很好地符合.作为算例，计算了W，Au，Rn，Am等元素的原子能量、熵及定容热容. 关键词： 自洽场原子结构 原子能量