密度泛函理论研究Pu+O2反应机理及键的特点

通过建立Pu与O2反应的理论模型,采用密度泛函理论(DFT)系统研究了钚原子与氧气分子的微观反应机理。优化了反应势能面上各驻点的几何结构,并用频率分析方法和内禀反应坐标(IRC)方法验证了过渡态,得到了该反应的反应势能曲线和微观反应路径。此外,用分子中的原子理论（AIM）和电子定域函数(ELF)理论方法探究了反应过程中各原子间化学键的演化特点。结果表明,这一反应体系有两条不同的反应路径,反应产物分别是PuO2和PuO+O; 能量分析表明,生成PuO2的反应更容易发生。     

密度泛函理论研究Pu+O_2反应机理及键的特点

通过建立Pu与O_2反应的理论模型,采用密度泛函理论(DFT)系统研究了钚原子与氧气分子的微观反应机理.优化了反应势能面上各驻点的几何结构,并用频率分析方法和内禀反应坐标(IRC)方法验证了过渡态,得到了该反应的反应势能曲线和微观反应路径.此外,用分子中的原子理论(AIM)和电子定域函数(ELF)理论方法探究了反应过程中各原子间化学键的演化特点.结果表明,这一反应体系有两条不同的反应路径,反应产物分别是PuO_2和Pu O+O;能量分析表明,生成PuO_2的反应更容易发生.     

Electronic structure and fluorescence spectrum of the HeO+ cation

Quantum-mechanical calculations of the potential curves of the HeO⁺ ion are preformed which correlate with four lower dissociation limits and indicate the excimer type of the ion. The transition dipole moments of the 2²Σ^?→1²Σ^? and 2⁴Σ^?→1⁴Σ ^? transitions are calculated. The energies and radiative lifetimes of vibrational levels are determined and structural and spectroscopic constants of the states 1²Σ^?, 2²Σ^?, 1⁴Σ^?, and 2⁴Σ^? are calculated. The fluorescence spectrum corresponding to the 2²Σ^?→1²Σ^? and 2⁴Σ^?→1⁴Σ ^? transitions is also calculated. The possibility of lasing at these transitions is discussed.     

Chemiluminescent GeCl4 + O2 + Ar/He/Reactions

A chemiluminescent flame was produced in the reaction between GeCl₄ and an excited mixture of argon or helium with oxygen. Spectra of the reaction products were recorded and studied. Relative populations of the products in analyzed electronic, vibrational and rotational states corresponded to different temperatures.     

低速多电荷态离子He2+、O2+和Ne2+与W靶表面相互作用的动能电子发射研究

本文报道了He2 ,O2 和Ne2 与W靶表面相互作用中的动能电子产额随离子入射速度变化的实验测量结果.结果表明:在本实验的入射速度范围内,对同一入射离子,动能电子产额随入射离子的速度增大而线性增加.基于动能电子发射的机理,我们分析了影响动能电子产额的因素,理论上得出动能电子产额与入射速度增长呈线性增加的关系,取得了实验上和理论上一致的结果.     

A theoretical study of the structures and stabilities of N4O2 isomers

Five N₄O₂ isomers and their possible decomposition pathways were investigated with Møller–Plesset perturbation theory (MP2) and density functional theory (DFT). The most stable isomer is the open-chain C_2v structure, which has not been reported before. For all five N₄O₂ isomers, dissociation energies and eight transition states were studied in the present paper. The open-chain isomer 1 and the planar (C_2h) isomer 3 could be potential candidates for high energy density materials (HEDM) due to their large dissociation energy and moderate dissociation barrier.     

He+H+2及其同位素取代反应的立体动力学研究

运用准经典轨线方法,基于AQUILANTI势能面, 在碰撞能为145 kJ/mol时,对He+H⁺₂及其同位素取代反应的立体动力学性质进行了理论研究.对k-j′两矢量相关和k-k′-j′三矢量相关的分布函数,以及产物转动取向参数进行了详细的讨论.结果表明,He+HH⁺→HeH⁺+H,He+HD⁺→HeH⁺+ 关键词： 矢量相关 立体动力学 准经典轨线方法     

N2O+离子A2∑+电子态的光解动力学研究

用一束波长为360.55nm的激光,通过N2O分子的(3+1)共振多光子电离(REMPI)过程制备纯净且布居完全处于X2Ⅱ(000)态的母体离子N2O+,然后用另一束波长在275-328nm范围内的可调谐激光将制备的N2O+离子激发至预解离电子态A2∑+.实验发现,由于解离碎片NO+所具有的一定的反冲速度,其TOF质谱峰明显比N2O+母体宽.通过分析NO+碎片TOF质谱峰形状,得到了解离产物的总平均平动能;通过考察随光解能量的变化,发现光解能量在32000cm-1附近约250cm-1的变化范围内,值由约8000cm-1突然减小至约1600cm-1.通过分析,在光解能量小于32000cm-1的区域,解离通道为NO+(X1∑+)+N(4S);而在光解能量大于32000cm-1的区域,另一个具有较高解离限的解离通道,NO+(X1∑+)+N(2D),开启并完全取代N(4S)通道成为解离的惟一通道.根据实验结果,对在所研究的光解能量范围内的N2O+离子A2∑+电子态预解离机理进行了探讨.     

A comparative nearside-farside analysis of the He–N2 + and He–N2 inelastic collisions

A comparative study of the inelastic scattering of ¹⁴N₂ ⁺ and ¹⁴N₂ in collision with ³He atoms is presented. The unrestricted nearside-farside (NF) method proposed by Connor [J. Chem. Phys. 104, 2297 (1995)] is applied to analyse the Close Coupling rotationally state selected angular distributions for four kinetic energies. These four energies illustrate different regimes of the dynamics. The relationships between the structures of the calculated differential cross-sections (DCS) and the different regions of the potential energy surfaces involved which can be extracted from semi classical models are here easily obtained from a simple reading of the (NF) figures. At the higher energy far-off the wells (1000 cm^-1) the shape of the DCS are quite similar for the two systems and their nearside-farside components also, showing that the inelastic process is controlled by the short range repulsive part of the potential which is essentially the same for these two collisions. When the energy is decreased the differences between the two wells associated with the He–N₂ ⁺ and He–N₂ complexes are responsible for the differences between the DCS for the two systems. The farside component associated with the well become more and more prominent for the elastic scattering while inelastic scattering remains controlled by the repulsive core in a large angular interval. The nearside farside analysis gives also a new picture of a resonance which is regarded as an equilibrium between the repulsive and the attractive parts of the potential.     

O3+与氦原子碰撞过程的CTMC计算

应用经典径迹蒙特卡罗方法研究了O3+离子与氦原子碰撞的各种反应过程.基于使用多个系统总能量U值,对初始电子的微正则分布进行了优化,使其更接近于量子力学的径向空间分布.作为检验,首先在独立电子模型近似下计算了He2+与氦原子碰撞的各种反应过程,通过与实验的比较,发现对氦原子靶,优化极大地提高了计算精度.计算了O3+与氦原子随入射离子能量变化的各种反应过程截面,特别是单电子丢失、双电子丢失的总截面,以及转移电离截面与单俘获截面的比值,并与实验进行了比较,发现单双电子丢失截面与实验符合得很好,但在大于200 keV/u的能区,转移电离截面与单俘获截面的比值与实验有较大的差距,这表明独立电子模型需要进一步改进.     

Al2O3:Fe3+体系晶格局域结构的EPR理论研究

本文通过分析Al2O3∶Fe3+体系中Fe3+离子的EPR谱,研究Fe3+的局域晶体结构结果表明Al2O3∶Fe3+的局域结构存在各向异性膨胀.用拟合EPR谱的低对称参量D和(a-F)实验值的方法,求得两个三棱锥的棱与C3轴的夹角分别为θ1=46.54°和θ2=61.26°,相对于原Al2O3结构的畸变角分别是Δθ1=-1.1°±0.1°,Δθ2=-1.8°.两畸变角同时均小于0说明Al2O3∶Fe3+体系中含Fe3+离子的晶格主要产生沿C3轴的伸长畸变.     

An Investigation of 4He+12C and 4He+16O Reactions Using the Cluster Model

The α -target semimicroscopic single folding potentials have been derived by folding a composite (repulsive and attractive) effective α-α interaction with the α -cluster distribution density in the target nuclei. The obtained potentials are considered as the real part of the nuclear optical model potentials, while the imaginary parts are phenomenologicaly expressed using the Woods-Saxon form. Nine sets of measured experimental data of the ⁴He+¹²C and ⁴He+¹⁶O elastic rainbow scattering over the energy range 80-240 MeV are analyzed using the obtained potentials. The data are successfully reproduced using the extracted potentials. The resulted reaction cross sections are also investigated and compared with the available corresponding data.     

Experimental and numerical studies of the electron distribution function in He + O2 dc discharge

Probe measurements of the electron energy distribution in He + O₂ mixture discharge are compared with the results obtained using the Holstein form of the Boltzmann equation. The transport and Townsend coefficients are calculated and in case of pure helium and oxygen they are verified by available experiments. The results are presented for dc discharge over the range 0 to 30% of oxygen admixture in helium and 5×10^?17≦E/N≦2×10^?15 V cm².     

Pionic fusion study of the halo nucleus 6He, the reaction d+4He→6He+π + at CELSIUS

The halo nucleus ⁶He has been studied in a pionic fusion experiment at the CELSIUS storage ring facility in Uppsala. The ⁶He nuclei were produced in reactions with a deuteron beam incident on a ⁴He jet target 0.9–5.4 MeV above threshold in the center-of-mass frame. The ⁶He ions were detected in a ΔE-E solid-state detector telescope inserted into the CELSIUS ring. The aim of the experiment was to investigate, in particular, the high-momentum part of the halo wave function by measuring the total and differential cross sections of the reaction d+⁴He→⁶He+π ⁺.     

Quartet states of He+ 2

The low lying quartet spectrum of the molecular helium cation is investigated by configuration interaction calculations. Using large Gaussian basis sets, potential energy curves for n ⁴Σ⁺ _u,g and n ⁴Π_u,g are computed for the states n = 1,…, 5. Several of these states lead to equilibrium configurations having rather extended bond lengths and some of them also a relatively large dissociation energy. The spectroscopic properties of these equilibrium configurations are studied. Quartet He⁺ ₂ is most strongly bound in its lowest state 1 ⁴Σ_u with R _e = 3.424 Å and D _e = 1.348 eV.     

用紧耦合方法研究C4+和O6+与He原子碰撞

用双中心原子轨道紧耦合方法计算了C4+-He以及O6+-He碰撞的单俘获总截面,入射离子的能量范围为10～100keV/amu,所得计算结果在实验误差范围内与实验值很好符合.对满壳层入射离子,研究了单俘获截面随入射离子电荷态的变化,并讨论了原子轨道展开波函数数目对计算结果的影响.p     

Long-lived diatomic dications: potential curves and radiative lifetimes for CaBr2+ and CaI2+ including relativistic effects

Relativistic effective core potential calculations have been employed in the framework of a spin–orbit configuration interaction to compute the lowest-lying electronic states of the CaBr²⁺ and CaI²⁺ dications, and the results are compared with the data for the isovalent CaCl²⁺ system studied earlier. The ground X²Π state in all three dications arises from a strong polarization of X(²P°)(X= Cl, Br or I) by the Ca²⁺(¹S) ion and is bound by 0·96–1·55eV with respect to the corresponding diabatic dissociation limits. It is split by the spinorbit interaction into the X₁ ²Π_3/2 and X₂ ²Π_1/2 components, with the energy splittings calculated to be 647 cm^-1(CaCl²⁺), 2115 cm^-1(CaBr²⁺) and 3544 cm^-1(CaI²⁺). The X₁ and X₂ states are found to be thermodynamically stable in CaCl²⁺ and CaBr²⁺, while in CaI²⁺ the lowest dissociation limit, Ca⁺+(²S)+ I^{+ 3}P₂), lies 1700 and 5200 cm^-1 lower than the X₁ and X₂ minima respectively. The X₁ and X₂ states in CaI²⁺ are extremely long-lived, however, owing to the high and very broad potential barriers to dissociation. The first electronic excited state, A²σ⁺, is also bound in all the above systems, although it is pre-dissociated in CaBr²⁺and CaI²⁺ at large internuclear distances. All other low-lying electronic states of CaX²⁺ are repulsive. Electric-dipole moments are calculated for the A→ X₁, X₂ transitions. The corresponding radiative lifetimes are found to be very long in CaCl²⁺ : τ(A→X₁) = 19·3 ms and τ(A→X₂) = 9·9 ms (the values are given for ν' = 0), and become very significantly shorter for CaBr²⁺ and CaI²⁺ because of the stronger spin-orbit interaction in the heavier systems. This effect is especially noticeable for the A →X₂ transitions, for which the values are computed to be 364 μs in CaBr²⁺ and 50·3 μs in CaI²⁺. The theoretical data obtained should aid in the future spectroscopic detection of these species. To data no experiment of this type has been successfully carried out for any of the thermodynamically stable diatomic dications.     

Some bound states for the He2 2+ ion

Accurate potential energy curves for the lowest excited state of ¹Σ _g ⁺ symmetry and for the lowest state of ¹Σ _u ⁺ symmetry have been determined for the He₂ ²⁺ ion. The most flexible variational wavefunction used contained 153 linear and two non-linear parameters. The basis functions explicitly included interelectronic dependence and were constructed so that they led to the correct form for the dissociation products. The results are considered to be more accurate than those hitherto published. As well, and for the first time, the rovibronic energies for the two states were calculated.