Vibronic coupling in the first four electronic states of CH2F+2

Vibronic coupling in the energetically lowest first four electronic states of CH₂F⁺₂ is studied in this paper. A model 4×4 Hamiltonian is constructed in a diabatic electronic representation employing normal coordinates of vibrational modes and standard vibronic coupling theory. Extensive ab initio quantum chemistry calculations are carried out to determine the parameters of the Hamiltonian and energetic ordering of the electronic states. The topographical features of the latter are examined at length and several conical intersections are established. Nuclear dynamics calculations on coupled electronic states are carried out from first principles by propagating wave packet. Theoretically calculated broad band vibronic structure of the four states are found to be in good accord with the experimental results.     

The changes in electronic structure and optical properties of magnetic semiconductors at magnetic phase transitions

The influence of magnetic phase transitions on electronic structure and optical properties of magnetic semiconductors is discussed. Europium chalcogenides and chromium chalcogenide spinels are the main subjects of the investigation. It is shown, that many-body effects are responsible for the changes of optical properties and non-rigid band behavior of electronic structure. Magnetic phase transition leads to energy shift of wide bands and change in density of states of “magnetic” d(f)-electrons without any significant shift of their energies. The influence of fluctuations at T ～ T _c and antiferromagnetic semiconductors are also considered.     

The Pressure-Induced Shifts of Energy Spectra of ZnS:Ni2+

The calculations of the whole energy spectrum of Zns:Ni²⁺ at normal pressure and pressure-induced shifts of its levels have been carried out on the basis of the theory of pressure-induced shifts and the diagonalization of the complete d⁸ energy matrix in a regular tetrahedral field. The calculated results are in very good agreement with experimental data at normal and high pressures. The comparison between the results of ZnS:Ni²⁺ and Mg0:Ni²⁺ indicates that the comlency of ZnS:Ni²⁺ is obviously stronger than the one of MgO:Ni²⁺;the expansion of electron wavefunctions of ZnS:Ni²⁺ under pressure is obviously larger than that of MgO:²⁺; and the pressure-induced shifts of levels of znS:NiZf show strong nonlinearity.     

EPR and optical spectra of Ni2+-VAg in silver chloride and silver bromide

The optical absorption and EPR spectra of Ni²⁺-V_Ag centres in the AgCl:Ni²⁺ and AgBr:Ni²⁺ systems have been investigated theoretically on the basis of the complete energy matrices including the electron–electron repulsion interaction, the ligand field interaction, the spin–orbit coupling interaction, and Zeeman interaction. Because the charge compensation forms a silver ion vacancy (V_Ag) which makes the attractive force acted on the each ligand ion different, it was determined that the Ni–X (X = Cl, Br) distance next to V_Ag is shorter than others for both AgCl:Ni²⁺ and AgBr:Ni²⁺ systems in the tetragonal symmetry. Besides, it was found that the local lattice structure of (NiX₆)^4? clusters in AgCl and AgBr crystals exhibit a compression distortion. This compression distortion may be ascribed to the fact that the Ni²⁺ ion has a smaller ionic radius and more effective charge than the Ag⁺ ion.     

晶体Zn(antipyrine)2(NO3)2:VO2+的EPR谱及光吸收谱的理论研究

由于硝酸钒锌二安替比林晶体[Zn(antipyrine)2(NO3)2:VO2 ]中配体O2-的自旋-轨道耦合参量ζ0p≈150 cm-1与中心过渡族3d1离子V4 的ζ0d≈248 cm-1相差不太大,故配体的自旋-轨道耦合参量ζ0p对电子顺磁共振(EPR)谱和光吸收谱的贡献必须考虑.采用双自旋-轨道耦合参量模型和相关的晶体场能级公式,计算了Zn(antipyrine)2(NO3)2:VO2 晶体的EPR谱和光吸收谱,所得理论结果与实验发现很好符合;确定了该晶体的局域对称结构沿C4轴的四角畸变约为0.45 nm;计算发现,较大的κ值说明VO2 中未配对的s电子对超精细结构常数有较大的贡献.并对上述这些结果的合理性进行了讨论.     

气相吡啶分子S1态的(2+3)偏振共振多光子电离谱研究

利用气相吡啶分子分别在圆偏振光激发和线偏振光激发下的（２＋３）偏振共振多光子电离（ＰＲＭＰＩ）谱,对其第一激发态（Ｓ１）上的振转结构进行了研究。在谱中观察到了呈双峰结构的电子振转跃迁谱带。分析表明,所有振动谱带均为Ｓ１态上Ｖ６ａ、Ｖ１０ａ、Ｖ１２、Ｖ１６ｂ和Ｖ１７ａ以及基态上Ｖ９ａ的混合频率谱带。旨认吡啶Ｖ１７ａ的Ｓ１态频率为６７０ｃｍ＾－１,并认为在Ｓ１态上Ｖ７ａ频率降低的原因与Ｖ１０ａ类似。     

Low Temperature Spectra of the ortho-POPOP Molecule: Additional Arguments of Its Flattening in the Excited State

Low temperature absorption and fluorescence spectra were measured for 1,2-bis-(5-phenyl-oxazolyl-2)-benzene (ortho-POPOP), a sterically hindered molecule, substantially non-planar in its ground state. Quantum-chemical calculations with the optimization of molecular geometry were made using the semiempirical AM1 method. The observed spectral changes, together with the obtained theoretical results, evidenced in favor of our previously made assumption about the considerable flattening of ortho-POPOP in the lowest singlet excited state. The data of spin-orbit coupling between singlet and triplet terms, which has been estimated in CNDO/S scheme, were used to calculate the efficiency of intersystem crossing in the studied molecule.     

Expansions for One Quasiparticle States in Spin 1/2 Systems

Convergent expansions of the wavefunctions for the ground state and lowlying excited states of quantum transverse Ising systems are obtained. These expansions are employed to prove that the dispersion relation for a single quasi-particle has a convergent expansion.     

用光谱和EPR谱确定CsMgBr3:Ni2+的局域结构

本文采用半自洽场(semi-SCF)自由Ni2 的3d轨道波函数、点电荷—偶极子模型和Ni2 -6X-(X=F,Cl,Br,I)络合物的μ-κ-α模型,建立了结构参数与光谱、EPR谱之间的定量关系,利用完全对角化方法,由光谱和电子顺磁共振(EPR)谱,确定了CsMgBr3:Ni2 晶体在77K温度时的局域结构参数,统一解释了CsMgBr3:Ni2 晶体的局域结构、光谱和EPR谱。所得理论结果与实验值符合得很好。此外,还讨论了晶体局域结构发生畸变的原因。     

The resonance and pre‐resonance Raman scattering in the low energy 11B2u and 11B3u states of 1,4,5,8‐naphthalenetetracarboxy dianhydride in terms of DFT methods. The aggregation of NTCDA molecules in the ethanol and methanol solutions

The absorption, pre‐resonance, and resonance Raman spectra of 1,4,5,8‐naphthalenetetracarboxy dianhydride (NTCDA) molecule are examined in terms of time‐dependent density functional theory at TD‐B3LYP/aug‐cc‐pVDZ and TD‐SVWN/aug‐cc‐pVDZ levels. The Franck–Condon analysis performed for two 1¹A_g → 1¹B_2u and 1¹A_g → 1¹B_3u overlapping transitions leads to an excellent agreement between the theoretical predictions and experimental data providing that the calculated absorption is confronted with that measured in chloroform or acetonitrile but not in the ethanol (methanol) solution. We argue that absorption spectra measured in ethanol solution already known in literature do not characterize NTCDA molecule. On the basis of the absorption and resonance scattering spectra, we may deliberate that the dimerization of NTCDA is responsible for utterly different absorption observed in ethanol (methanol) comparing with less active solvents (chloroform and acetonitrile). That conclusion is supported by the dimer vibronic theory and by the TD‐B97d computations at the aug‐cc‐pVDZ basis set level. Copyright © 2013 John Wiley & Sons, Ltd.     

太阳光谱方法测量成都地区大气二氧化氮浓度

文章报道的是用太阳光谱方法测量成都地区NO2浓度的实验研究,使用CCD光学多道分析器采集成都市区和西岭雪山的太阳光谱,以大气上界太阳光谱为参考,对五个分立光谱段以最小二乘法进行数据拟合,应用差分吸收原理解谱,获得了成都市区和西岭雪山NO2浓度.成都市区NO2浓度(垂直柱体密度)在3.1×1016至5.8×1016(molecule·cm-2)之间,西岭雪山的NO2浓度在0.7×1016至1.0×1016(mole-cule·cm-2)之间.随大气温度的上升,NO2浓度有上升趋势.     

Spin coupling and magnetic field effects on the finite-size free energy and its non-extensivity for 1-D Ising model with nearest and next-nearest neighbor interactions in nanosystem

The effects of second-neighbor spin coupling interactions and a magnetic field are investigated on the free energies of a finite-size 1-D Ising model. For both ferromagnetic of nearest neighbor (NN) and next-nearest neighbor (NNN) spin coupling interactions, the finite-size free energy first increases and then approaches a constant value for any size of the spin chain. In contrast, when NNN and NN spin coupling interactions are antiferromagnetic and ferromagnetic, respectively, the finite-size free energy gradually decreases by increasing the competition factor and eventually vanishes for large values of it. When a magnetic field is applied, the finite-size free energy decreases with respect to the case of zero magnetic fields for both ferromagnetic and antiferromagnetic spin coupling interactions. Deviation of free energy per size for finite-size systems relative to the infinite system increases when the spin coupling interactions as well as the f parameter (the ratio of the magnetic field to NN spin coupling interaction) increase.     

有限核真空中的反核子能谱

通过建立能够自洽地描述核子和反核子束缚态的相对论Hartree模型来研究有限核中的量子真空,其中狄拉克海对介子场方程的贡献由单圈图考虑,模型中还引入了ω介子和ρ介子的张量耦合项.在拟合球形核的性质后得到模型的参数,给出核子有效质量为m*/MN≈0.78;计算得到的核子壳模型能级与实验值相一致,在考虑张量耦合项的效应后真空反核子位阱深度增大了20—30MeV.     

原子轨道强耦合方法研究He2+-H-碰撞的电荷转移过程

应用双中心原子轨道强耦合方法研究He²⁺-H^-碰撞的单次电荷转移过程.计算中,对入射粒子He²⁺,包含n=1~7的所有束缚态,计算的能量本征值与NIST标准数据在百分之几的精度内符合很好;对靶H^-,包括一个束缚态1s和五个连续态ns(n=2~6),束缚态能量与他人理论结果一致.在4~400 keV的入射粒子能量范围,计算单电子俘获过程的总截面及到各个壳层上的态选择截面.发现在较低的入射粒子能量,电子主要俘获到He⁺离子主量子数n=3~5的壳层,高能区俘获到n=2的壳层为主;对同一主量子数n,在低能区俘获到高角动量态(l=n-1,n-2)的电荷转移截面相对较大,在高能区主要俘获到l=1的p壳层.同时还计算入射粒子能量分别为4 keV和400 keV时,电子俘获到激发态辐射退激发产生的电荷转移发射光谱,并发现cascade效应的影响很大.     

晶体PZCST:VO2+的EPR谱及光吸收谱的理论研究

采用双旋-轨耦合参量模型和3d¹电子组态在四角对称下的能级公式,计算了KZnClSO₄·3H₂O(PZCST): VO²⁺的EPR谱和光吸收谱,所得EPR谱和光吸收谱的理论结果与实验发现符合得很好. 研究发现,该晶体沿C₄轴局域对称结构呈压缩的四角畸变,其大小为0.47 nm;大的κ值表明VO²⁺的未配对电子的自旋极化对超精细结构常数有着较大的贡献.     

Ar2H+ 分子振动光谱的理论计算

基于近期由本组提供的Ar2 H+ 分子的基态势能面 ,应用含时波包演化方法 ,计算了总角动量J =0时的振动光谱 ,并对其中的一些谱峰进行了指认 .与现有的abinitio结果进行比较 ,这个新势能面包含了关于Ar2 H+ 基态的比较正确的信息     

Theoretical studies of absorption spectra and microstructure of Ni2+ at the octahedral site of the NiFe2O4 nanoparticle

The optical absorption spectra, microstructure and electronic spin resonance parameters (electronic spin resonance (ESR) g factor) for Ni²⁺ ions at octahedral centers of nickel ferrite nanoparticles are calculated from the two-spin–orbit-parameter model. The effect of spin–orbital coupling of the central metal 3d⁸ ions and ligand oxygen ions has been taken into account in the full energy matrix and ESR g formula. The calculated results are in good agreement with the observed values. In addition, the microstructures of Ni²⁺ ions at octahedral centers in NiFe₂O₄ are reasonably determined from the calculations.     

Eu3+摩尔浓度对Y2O2S:Eu3+,Mg2+,Ti4+红色长余辉材料光谱的影响

用高温固相法制备了Y2O2S：Eu^3 ,Mg^2 ,Ti^4 红色长余辉材料。测量了该材料的余辉曲线,余辉时间为1h以上;由X射线衍射得到晶体结构为Y2O2S.测量了不同Eu^3 摩尔浓度下的激发光谱和发射光谱,得到从^5DJ(J=0,1,2,3)^-7FJ(J=0,1,2,3,4,5)的发射谱线,并得到位于260,345,468和540nm激发峰。由于激活剂饱和效应,Y2O2S：Eu^3 ,Mg^2 ,Ti^4 发射光谱中513．6,540．1,556．4,587．3和589．3nm属于从^5D2,^5D1到^7FJ(J=0,1,2,3,4)跃迁的发射峰随Eu^3 摩尔浓度的增加相对削弱;激发谱包括位于350nm左右属于电荷转移态吸收(Eu^3 -O^2-,Eu^3 -S^2 )的激发主峰和在可见光区位于468,520和540nm属于Eu^3 离子4f-4厂吸收的激发峰。随着Eu^3 摩尔浓度的增加,位于468,520和540nm的激发峰相对增强。     

CuAlS2∶Ni+晶体光谱和电子顺磁共振谱研究

Ni 离子在三元化合物CuAlS2半导体中替代离子Cu .应用晶体场理论,结合CuAlS2中Cu 位置的结构数据,计算了CuAlS2∶Ni 晶体的光谱和电子顺磁共振谱(g因子和超精细结构常数),计算结果与实验值符合得很好.     

Critical temperature studies of the anisotropic bilayer and multilayer Heisenberg ferromagnets in Pair Approximation

The Pair Approximation method is applied to studies of the bilayer and multilayer magnetic systems with simple cubic structure. The method allows to take into account quantum effects related to non-Ising couplings. The paper adopts the anisotropic Heisenberg model for spin S=1/2 and considers phase transition temperatures as a function of the strength of exchange integrals in line with the role of intra- and interplanar anisotropic interactions in the onset of low-dimensional magnetism. The compensation effect for the Curie temperature is found for asymmetric interactions within the neighbouring planes of the bilayer system. The paper predicts the saturation of the Curie temperature for strong interplanar interactions. However, such an effect for the multilayer system occurs only when the interplanar interactions are purely of isotropic character.