Ab initio dipole polarizabilities and quadrupole moments of the lowest excited states of atomic Yb

The finite-field scalar relativistic coupled cluster and configuration interaction, as well as the spin-orbit configuration interaction, methods are employed to calculate the static dipole polarizabilities for the lowest (6s ²) ¹S, (6s6p) ^1,3^{1,3}P^o and (6s5d) ^1,3^{1,3}D excited states of atomic ytterbium. The results agree very well with existing experimental and best theoretical data and refine the set of ytterbium polarizabilities known so far. Similar techniques are used to calculate the electric quadrupole moments for the ^1,3^{1,3}P^o and ^1,3^{1,3}D states.     

Doubly excited 2s2p 1,3P1 resonances in photoionization of helium

The multi-configuration Dirac-Fock（MCDF） method is implemented to study doubly excited 2s2p ^1,3P₁ resonances of the helium atom and the interference between photoionization and photoexcitation autoionization processes.In order to reproduce the total photoionization sprectra,the excited energies from the ground 1s^{2 1}S₀ state to the doubly excited 2s2p ^1,3P₁ states and the relevant Auger decay rates and widths are calculated in detail.Furthermore,the interference profile determined by the so-called Fano parameters q and ρ² is also reproduced.Good agreement is found between the present results and other available theoretical and experimental results.This indeed shows a promising way to investigate the Fano resonances in photoionization of atoms within the MCDF scheme,although there are some discrepancies in the present calculations of the 2s2p ³P₁ state.     

Doubly Excited <Superscript>1,3</Superscript><Emphasis Type="Italic">P</Emphasis><Superscript>e</Superscript> Resonance States of the Positronium Negative Ion with Coulomb and Screened Coulomb Potentials

We have investigated the doubly excited ^1,3 P ^e resonance states of positronium negative ion with Coulomb and screened Coulomb potentials using highly accurate correlated exponential wavefunctions. For Coulomb interaction, the stabilization and the complex-rotation methods are employed to extract resonance parameters (resonance positions and widths). We have obtained two ¹ P ^e resonances and three ³ P ^e resonances below the n = 3 Ps threshold. In addition to Feshbach resonances lying below n = 3 Ps threshold, we have calculated one ³ P ^e shape resonances lying above the Ps (n = 2) threshold. For screened Coulomb (Yukawa) interaction, we employ the stabilization method to extract resonance parameters as functions screening parameter. The resonance energies and widths for ^1,3 P ^e resonance states of Ps⁻ below the n = 3 Ps threshold for different screening parameters ranging from infinity (Coulomb case) to small values are reported, along with the Ps(3S) and Ps(3P) threshold energies. The screened Coulomb results for the ^1,3 P ^e resonance states are reported for the first time in the literature.     

镁原子碰撞激发微分截面和Stokes参数的理论研究

基于相对论扭曲波理论方法,并利用新发展的处理极化电子碰撞激发的计算程序REIE06, 系统计算了中性镁原子基态3s^{2 1}S₀到激发态3s3p ¹P₁, 3s4p ¹P₁的电子碰撞激发微分截面和角关联(Stokes)参数,计算过程中系统地考虑了相对论效应、电子关联效应等. 部分计算结果与已有的实验和理论结果进行了比较,得到了较好的一致性.     

Autoionization states of the beryllium atom

Using the modified Feshbach method, the^1,3S^e,^1,3P^o,^1,3D^e,^1,3S^o autoionization states of the beryllium atoms are calculated in the region of the first ionization threshold. The energies and widths of the autoionization states of Be are obtained. The results obtained are compared with experimental data and the results of existing theoretical calculations. The good agreement between the results obtained and the experimental data and other theoretical calculations is pointed out.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 23–28, March, 1984.     

Fine-structure energy levels,oscillator strengths and lifetimes in Mg-like chromium

Excitation energies from ground state for 86 fine-structure levels as well as oscillator strengths and radiative decay rates for all fine-structure transitions among the levels of the terms (1s²2s²2p⁶)3s²(¹S), 3s3p(^1,3P^o), 3s3d(^1,3D), 3s4s(^1,3S), 3s4p(^1,3P^o), 3s4d(^1,3D), 3s4f(^1,3F^o), 3p²(¹S, ³P, ¹D), 3p3d(^1,3P^o, ^1,3D^o, ^1,3F^o), 3p4s(^1,3P^o), 3p4p(^1,3S, ^1,3P, ^1,3D), 3p4d(^1,3P^o, ^1,3D^o, ^1,3F^o), 3p4f(^1,3D, ^1,3F, ^1,3G) and 3d²(¹S, ³P, ¹D, ³F,¹G) of Cr XIII are calculated using extensive configuration-interaction (CI) wave functions obtained with the CIV3 computer code of Hibbert. The important relativistic effects in intermediate coupling are included through the Breit-Pauli approximation via spin-orbit, spin-other-orbit, spin-spin, Darwin and mass correction terms. Small adjustments to the diagonal elements of the Hamiltonian matrices have been made. The mixing among several fine-structure levels is found to be very strong. Our excitation energies, including their ordering, are in excellent agreement (better than 0.5%) with the available experimental results. From our transition probabilities, we have also calculated radiative lifetimes of some fine-structure levels. Our calculated lifetime for the longer-lived level 3s3p(³P₁) is found to be in excellent agreement with the experimental result of Curtis compared to other theoretical calculations.     

Numerical Simulation of Ne–Tl and Ne–Ga Ion Hollow-Cathode Lasers

Results of theoretical and experimental studies of the behavior of the level populations and gain factors for the np ^1,3 P – ns ^1,3 S and np ^1,3 P –> (n-1)d ^1,3 D transitions in Tl II (n = 7) and Ga II (n = 5) are presented. These levels are filled due to the charge exchange in thermal collisions of neon ions with thallium and gallium atoms in thallium--neon and gallium--neon mixtures, respectively. The total pumping rate of all levels of a metal due to the charge exchange in the hollow-cathode discharge plasma at the operating concentrations of metal vapors was shown to be equal to the gas ionization rate. The latter is defined by the number of fast electrons and is independent of the charge-exchange cross section. The exciting and deexciting collisions with slow electrons and gas atoms were taken into account for all Tl II and Ga II levels related to the laser ones, and the radiation trapping by the resonance transitions of metal ions was considered. The partial pumping rates by the charge exchange were found for levels with 0 < E() < 1.5 eV. Theoretical results are compared with experimental data. The behavior of the lasing characteristics is explained for the known laser transitions. The parameters of the as yet unknown transitions in the IR range are predicted.     

Hyperfine-structure studies of the 1s<Superscript>2</Superscript>2snp (n=2, 3) <Superscript>3</Superscript>P states for the beryllium isoelectronic sequence

The hyperfine structure parameters of the 1s²2snp (n=2, 3) ³P states for the beryllium isoelectronic sequence from Z= 4 to 10 are calculated with the full-core plus correlation (FCPC) wave functions. For the 1s²2s2p ³P state of the beryllium atom, the calculated fine structure parameters are in good agreement with the latest theoretical and experimental data in the literature. It is shown that hyperfine constants of the low-lying excited states for the beryllium atom can be calculated accurately using this theoretical method. For 1s²2snp (n=2, 3) ³P states of the beryllium isoelectronic sequence, our predictions may provide valuable reference data for other theoretical calculations and experimental measurements in future.     

Ne原子的1s光电离及其Auger衰变过程的理论研究

利用基于多组态Dirac-Fock理论方法的研究原子结构和性质的程序GRASP92和RATIP以及最新发展的研究光电离和辐射复合过程的程序RERR06,研究了光子能量为947.9 eV时Ne原子的1s光电子谱及其相应的Auger衰变过程.所得结果与其他的理论结果和实验结果符合得很好.通过分析光电离伴随态Ne⁺1s^-12p^-1（^1,3Ｐ）3p的Auger衰变过程可知：3p旁观的Auger跃迁是主要的衰变机制,Ne⁺1s^-12p^-1（¹Ｐ）3p的Auger强度整体上大于Ne⁺1s^-12p^-1（³Ｐ）3p的Auger强度.同时,也预言了光电离伴随态Ne⁺1s^-12p^-1（^1,3Ｐ）3p产生的Ne⁺,Ne²⁺和Ne³⁺末电离态离子的相对丰度分别为0.02,0.58和0.41. 关键词： 光电离 Auger衰变 多组态Dirac-Fock方法     

Optical spectra and spin-Hamiltonian parameters of trivalent ytterbium in lead tungstate

By using crystal-field theory, the optical spectra and spin-Hamiltonian parameters (abbr. SH parameters, i.e. the anisotropic g factors g _∥, g _⊥, and hyperfine structure constants A _∥, A _⊥) of ¹⁷¹Yb^3 + and ¹⁷³Yb^3 + isotopes in the tetragonal PbWO₄ are calculated. The theoretical results agree well with the experimental values. The crystal-field parameters and the signs of the hyperfine structure constants for both ¹⁷¹Yb^3 + and ¹⁷³Yb^3 + isotopes are determined. The validities of the theoretical results are discussed.     

Electronic states of CsLi and CsLi<Superscript>+</Superscript> molecules

Configuration interaction calculations have been carried out on electronic states of the CsLi molecule and the CsLi⁺ cation. Adiabatic potential energy, spectroscopic constants, dipole moments, and vibrational levels are presented for the lowest states of ^1,3Σ⁺, ^1,3Π, and ^1,3Δ symmetries of the alkali dimer CsLi molecule dissociating into Cs (6s, 6p, 5d, 7s, and 7p) + Li (2s, 2p, 3s, 3p, and 3d) as well as for the lowest ²Σ⁺, ²Π, and ²Δ electronic states of the CsLi⁺ cation dissociating into Li (2s, 2p, 3s, 3p, and 3d) + Cs⁺ and Li⁺ + Cs (6s, 6p, 5d, 7s, and 7p). The results of the present many-electron configuration interaction calculations on the cation support the previous core-polarization effective potential calculations. The present calculations on the CsLi molecule are complementary to previous theoretical work on this system, including recently observed electronic states that had not been calculated previously. We have used an ab initio approach involving a nonempirical pseudopotential for the Li (1s²) and Cs cores and a core-valence correlation correction. A very good agreement of data from spectroscopic constants for some of the lowest states of the CsLi and CsLi⁺ molecules with those available in recent theoretical works has been obtained. The existence of numerous avoided crossings between electronic states of ²Σ⁺ and ²Π symmetries is related to a charge transfer process between the two ionic CsLi⁺ and LiCs⁺ systems.     

Fine structure and centrifugal distortion in the electronic and microwave spectra of O2 and SO

The fine structure theory of ³Σ states in diatomic molecules is re-examined with particular emphasis on centrifugal distortion in the triplet splitting parameters. The theoretical results are compared with optical and microwave data for the ³Σ ground states of O₂ and SO. Excellent agreement is found between theoretical predictions and experimental results concerning the centrifugal distortion in the spin-spin splitting for both O₂ and SO. However, in contrast to ab initio calculations this agreement indicates that the second-order contribution to the spin-spin splitting is of minor importance. The theoretical value of the centrifugal distortion in the spin-rotation coupling constant is about twice the experimental one for O₂. It is pointed out that a slight transition towards coupling case (c) yields a reasonable explanation for this discrepancy.     

β-Si3N4电子结构和红外和拉曼频率的第一性原理研究

分别用PW91,B3LYP两种密度泛函方法和全电子高斯基组对β-Si₃N₄的几何结构进行全优化(包括晶格参数和原子坐标),结果和实验值符合良好. 同时计算了能带结构和态密度.在此基础上分别用上述两种方法计算了Γ点拉曼振动频率,并按对称性进行分类,将得到的11种拉曼活性模式的频率值与实验值以及其他文献值进行了比较,进一步确定了A_g模式为中等频率,值约459cm^-1. 计算结果表明 关键词： 振动频率 密度泛函理论 电子结构 3N₄')" href="#">β-Si₃N₄     

Calculation of fine structure parameters by semiempirical method from energy intervals between magnetic sublevels

A method is developed for the semiempirical calculation of fine structure parameters from the experimental energy intervals between magnetic sublevels. The calculations are performed using the configuration of neutral carbon as an example. The calculated parameters are used to calculate the 2p ² configuration energy spectrum and the gyromagnetic ratios of the ³ P ₂ and ¹ D ₂ levels, as well as the magnetic splitting of triplet levels. The results are compared with available experimental and theoretical data. It is confirmed that the dependence of the energy of magnetic sublevels of np ² configurations on the magnetic induction is parabolic for sublevels with the projections M = 0, ±1 and is linear for sublevels with M = ±2.     

BH分子基态和激发态解析势能函数和光谱性质

运用多参考组态相互作用的方法和Dunning’s相关调和基函数并含扩散基的大基组aug-cc-pV5Z,获得了BH分子基态（X¹Σ⁺）和6个电子激发态（a³П, A¹П, B¹Σ⁺, b³Σ⁺, b³ 关键词： 势能曲线 解析势能函数 多参考组态相互作用方法 光谱常数     

Quadrupole Oscillator Strengths of Helium Interacting with Debye Potentials

The influence of Debye potentials on the quadrupole oscillator strengths of helium atom is investigated using highly correlated wave functions within a framework of a variational method. The quadrupole oscillator strengths for the ^1,3S–^1,3D, ^1,3P–^1,3P and ^1,3D–^1,3D transitions of He for various screening parameters are reported for the first time in the literature. In free atomic case, our calculated results are in good agreement with the available results.     

磁电双层膜层间耦合的弹性力学研究

基于磁致伸缩相与压电相的本构方程,应用弹性力学模型,简要介绍了如何推导自由状态的磁电双层膜纵向、横向磁电(ME)电压系数. 并采用相应的材料参数计算了La_07Sr_03MnO₃-Pb(Zr,Ti)O₃ (LSMO-PZT),Tb_1-xDy_xFe_2-y(TDF)-PZT双层膜中的磁电电压系数,具体分析了其与压电相 关键词： 磁电效应 双层膜 TDF LSMO PZT     

First-principles investigation on vibrational,anisotropic elastic and thermodynamic properties for L12 structure of Al3Er and Al3Yb under high pressure

To better clarify the physical properties for Al₃RE precipitates, first-principles calculations are performed to investigate the vibrational, anisotropic elastic and thermodynamic properties of Al₃Er and Al₃Yb. The calculated results agree well with available experimental and theoretical ones. The vibrational properties indicate that Al₃Er and Al₃Yb will keep their dynamical stabilities with L1₂ structure up to 100 GPa. The elastic constants are satisfied with mechanical stability criteria up to the external pressure of 100 GPa. The mechanical anisotropy is predicted by anisotropic constants A^G, A^U, A^Z and 3D curved surface of Young’s modulus. The calculated results show that both Al₃Er and Al₃Yb are isotropic at zero pressure and obviously anisotropic under high pressure. Further, we systematically investigate the thermodynamic properties and provide the relationships between thermal parameters and pressure. Finally, the pressure-dependent behaviours of density of states, Mulliken charge and bond length are discussed.     

Unusual conformational preferences of 1,3‐dimethyl‐3‐isopropoxy‐3‐silapiperidine

The conformational analysis of the first representative of the Si‐alkoxy substituted six‐membered Si,N‐heterocycles, 1,3‐dimethyl‐3‐isopropoxy‐3‐silapiperidine, was performed by low‐temperature ¹H and ¹³C NMR spectroscopy and DFT theoretical calculations. In contrast to the expectations from the conformational energies of methyl and alkoxy substituents, the Me_axi‐PrO_eq conformer was found to predominate in the conformational equilibrium in the ratio Me_axi‐PrO_eq : Me_eqi‐PrO_ax of ca. 2 : 1 as from the ¹H and ¹³C NMR study. The thermodynamic parameters obtained by the complete line shape analysis showed that the main contribution to the barrier to ring inversion originates from the entropy term of the free energy of activation. Copyright © 2012 John Wiley & Sons, Ltd.     

CASPT2 and CCSD(T) calculations of dipole moments and polarizabilities of acetone in excited states

The acetone molecule is investigated in its ground state and valence ^1,3n-π*, ^1,3π-π*, and ^1,3σ-π* excited states and Rydberg ^1,3n-3s, ^1,3π-3?, ^1,3n-3p_y and ^1,3π-3p_y states using the CASSCF, CASPT2, and CCSD(T) methods. Equilibrium geometries of excited states are obtained and their changes with respect to the ground state are discussed. For most excited states the C_2v symmetry of the ground state is lowered to the C_s symmetry. A series of valence vertical and adiabatic excitation energies is presented along with excitation energies for Rydberg states. The main body of the paper contains Finite-Field Perturbation Theory (FFPT) calculations of electric properties of the vertically as well as geometry relaxed excited states. Dipole moments of valence excited states decrease significantly upon excitation, being about one half of the ground state dipole moment. Polarizabilities usually change upon excitation much less (increase by about 30%) but hyperpolarizabilities are enhanced up to one or two orders of magnitude. The orientation of the dipole moment is reversed in some vertically excited Rydberg states. Properties of the ground and excited states are discussed considering alterations of the electronic structure and shifts in the geometry.