Oscillator strengths for Rydberg states in ArH calculated in QDT approximation

With the help of a simple semi-analytical procedure the oscillator strengths for Rydberg electronic transitions in the ArH molecule are calculated by accounting for the effects of non-spherical symmetry of the molecular core’s field due to its dipole moment. Such effects result in non-zero oscillator strength values for some transitions which are forbidden in the widely used atom-like model of molecular Rydberg states. For the allowed transitions we also report the difference between the atom-like calculations and the calculations which take into account the dipole moment of the molecular core.     

Influence of solvent and intramolecular relaxation on dynamics of luminescence spectra in donor–acceptor complexes

The oscillator strengths for Rydberg states of a NaHe molecule are calculated using a semianalytic procedure with the l-coupling effect taken into account (due to the dipole potential of a core). This effect gives rise to nonzero oscillator strengths for transitions forbidden in the atomic model of molecular Rydberg states. The difference between calculations in terms of the atomic model and calculations with consideration of the dipole moment of a core is shown for allowed transitions.     

Mn22+离子1s22s-1s2np的偶极跃迁能和振子强度

用全实加关联方法计算了类锂Mn22 离子1s22s-1s2np(2≤n≤9)的偶极跃迁能和振子强度.1s2np(2≤n≤9)态的精细结构通过计算自旋-轨道与自旋-其他轨道相互作用算符的期待值确定.依据单通道量子亏损理论,确定了Rydberg系列1s2np的量子数亏损.从而可以用这些作为能量的缓变函数的量子亏损,实现对任意高激发态(n≥10)的能量的可靠预言.将这些分立态振子强度与单通道量子亏损理论相结合,得到在电离阈附近束缚态-束缚态跃迁振子强度以及束缚态-连续态跃迁的振子强度密度,从而将Mn22 离子的这一重要光谱特性的理论预言外推到整个能域.     

The 4s Orbital of Sulfur

The 4s orbital of sulfur has been studied by semiempirical calculations on the H₂S molecule. Overlap population, overlap energy, dipole moment, and oscillator strengths are computed as functions of the orbital exponent of the Slater type 4s orbital, with and without 3d orbitals. The 4s orbital contracts from what is expected for the free atom, but remains essentially Rydberg in character.     

Sc+18离子1s23d-1s2nf的跃迁能和偶极振子强度

用全实加关联方法计算了类锂Sc 18离子1s23d-1s2nf(4≤n≤9)的跃迁能和1s2nf(n≤9)态的精细结构。依据量子亏损理论确定了该Rydberg系列的量子数亏损,用这些作为能量的缓变函数的量子亏损,可以实现对任意高激发态(n≥10)的能量可靠的预言。利用在计算能量过程中确定的波函数,计算了Sc 18离子1s23d-1s2nf的偶极跃迁在三种规范下振子强度;将这些分立态振子强度与量子亏损理论相结合,得到在电离阈附近束缚态-束缚态跃迁振子强度以及束缚态-连续态跃迁振子强度密度,从而将Sc 18离子的这一重要光谱特性的理论预言外推到整个能域。     

Cr~(21+)离子1s~23d-1s~2nf的跃迁能和偶极振子强度(英文)

用全实加关联方法计算了类锂Cr21+离子1s23d-1s2nf(4≤n≤9)的跃迁能和1s2nf(n≤9)态的精细结构.在类氢近似下估算了对能量的高阶相对论修正.依据量子亏损理论,确定了Rydberg系列1s2nf的量子数亏损.据此可以实现对任意高激发态(n≥10)的能量的可靠预言.计算了Cr21+离子1s23d-1s2nf(4≤n≤9)跃迁的振子强度.与量子亏损理论相结合,得到该离子从1s23d态到电离阈附近高激发束缚态间的偶极跃迁振子强度以及到相应连续态跃迁的振子强度密度,从而将Cr21+离子的这一重     

V+20离子的能量和偶极振子强度

用全实加关联方法计算了类锂V+20离子 1s2nl(l=s,p, d;n≤9) 态的电离势和精细结构.依据单通道量子亏损理论, 确定了这三个Rydberg系列的量子数亏损.用这些作为能量的缓变函数的量子亏损,可以实现对任意高激发态(n≥10)的能量的可靠预言.用在计算能量过程中确定的波函数,计算了V+20离子1s22s-1s2np及1s22p-1s2nd (n≤9)跃迁的振子强度.将这些分立态振子强度与单通道量子亏损理论相结合,得到在电离域附近束缚态间的偶极跃迁振子强度以及束缚态-连续态跃迁的振子强度密度,从而将V+20离子的这一重要光谱特性的理论预言外推到整个能域.     

Transition energy and dipole oscillator strength for 1s22p-1s2nd of Cr2l+ ion

The transition energies, wavelengths and dipole oscillator strengths of 1s^22p-1s^2nd （3 ≤ n ≤ 9） for Cr^21＋ ion are calculated. The fine structure splittings of 1s^2nd （n ≤ 9） states for this ion are also calculated. In calculating energy, we have estimated the higher-order relativistic contribution under a hydrogenic approximation. The quantum defect of Rydberg series 1s^2nd is determined according to the quantum defect theory. The results obtained in this paper excellently agree with the experimental data available in the literature. Combining the quantum defect theory with the discrete oscillator strengths, the discrete oscillator strengths for the transitions from initial state 1s^22p to highly excited 1s^2nd states （n ≥ 10） and the oscillator strength density corresponding to the bound-free transitions are obtained.     

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Using the fully relativistic configuration interaction (RCI) method and the multi-configuration Dirac-Fock (MCDF) method and taking quantum electrodynamical (QED) effect and Breit correction into account, wavelengths, transition probabilities and oscillator strengths were calculated for electric dipole (E1) transitions and magnetic dipole (M1) transitions in Au⁵⁰⁺ ion. The obtained energy levels of some excited states and wavelengths of transitions in Au⁵⁰⁺ ion from the method were compared with other theoretical and experimental results, and a good agreement with other results was shown. The calculated transition probabilities and oscillator strengths in E1 transitions using the velocity and length gauges respectively confirmed the accuracy of our calculations. The calculation results indicated that for high-Z highly ionized atom, some forbidden transitions could be very important.     

强外电场作用下BF分子结构和激发特性

采用密度泛函(DFT)方法LSDA在6-311++G(d,p)基组水平上优化得到了分子轴方向不同电场(-0.03～0.05a.u.)作用下,BF分子的基态结构参数、电偶极矩μ、电荷分布、HOMO能级、LUMO能级等。在优化构型下,用同样的基组采用杂化CIS-DFT方法(CIS-LSDA)研究了同样外电场条件下对BF分子的激发能和振子强度的影响。结果表明:随着电场的增加,分子结构与外电场有着强烈的依赖关系,且对电场方向的依赖呈现非对称性。分子总能量先增大后减小,电偶极矩μ先增大,后减小,最后不断增大。电场对振子强度的影响比较复杂,有的增大有的减小,表明电子跃迁光谱强度受外场影响。     

Fe XVII离子能级和振子强度的相对论多组态Dirac-Fock计算

本文用相对论多组态的狄拉克-福克(Dirac-Fock)(MCDF)近似方法计算了铁的类氖离子FeXVII的2p~53s,和3p和3d态的所有能级以及3s—3p,3p—3d跃迁的电偶极振子强度f值.理论计算的能级值同实验值的比较表明,使用MCDF方法计算类氖等电子序列的能级会得到与实验值符合得比较好的结果.因无实验数据可作比较,本文得到的振子强度值纯属理论预言值.     

Transition probabilities, oscillator strengths and lifetimes for singly ionized magnesium

The electric dipole transition probabilities, oscillator strengths and lifetimes have been calculated using the weakest bound electron potential model theory (WBEPMT) for singly ionized magnesium. In the calculations both multiplet and fine structure transitions are studied. We have employed both the numerical Coulomb approximation (NCA) method and numerical non-relativistic Hartree-Fock (NRHF) wave functions for expectation values of radii. The calculated oscillator strengths and lifetimes have been compared with MCHF results given by Fischer et al. (2006). A good agreement has been obtained with the MCHF results. Moreover, some new transition probabilities, oscillator strengths and lifetime values, not existing in the data bases for highly excited levels in singly ionized magnesium, have been obtained using this method.     

Na原子高里德伯态的波函数和振子强度

用我们提出的一种具有解析解的原子唯象势模型, 计算了Na原子里德伯态(10≤n≤40)的波函数和ns--n'p ,np--n'd, nd--n'f 高里德伯态间的振子强度, 与以方法得到的结果很接近. 计算结果表明, 上述振予强度满足某种标度律. 关键词：     

Calculation of the spectra of potassium-like multicharged ions

The energy levels and oscillator strengths for dipole transitions between the levels of low-lying configurations are calculated for ions of the KI isoelectronic sequence. The calculations are based on the energy approach to the effective potential method with the most important polarization effects taken into account, including core polarization by the outer electron. The results, some of which are obtained here for the first time for potassium-like ions, can be useful in a number of related fields, such as laser physics, plasmas, and so on.Odessa Hydrometeorological Institute. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 3–9, November, 1992.     

Photoelectron and electronic absorption spectra of SCl2, S2Cl2, S2Br2 and (CH3)2S2

Photoelectron and electronic absorption spectra of SCl₂, S₂Cl₂, S₂Br₂, and (CH₃)₂S₂ have been measured and analyzed. Quantum chemical calculations (CNDO/ 2 and MWH (Mulliken-Wolfsberg-Helmholtz) have been carried out and the electronic structures have been described in terms of molecular orbital theory. The variation in differential photoionization cross-section as a function of incident photon energy and results of MO computations are used to identify ionization bands and assign ground state MO configurations. Suggested ground state electronic structures coupled with computed virtual MO's are used to interpret the visible and near-ultraviolet electronic absorption spectra. The low energy excited states are described as molecular states followed by the initial members of Rydberg series. Calculated oscillator strengths for molecular transitions are in good agreement with those observed experimentally. Quantum defects, δ, for the Rydberg states have been calculated from the Rydberg equation using the adiabatic first ionization potential.     

Na原子高里德伯态的波函数和振子强度

用我们提出的一种具有解析解的原子唯象势模型,计算了Na原子里德伯态(10≤n≤40)的波函数和ns—n＇p,np—n＇d,nd—n＇f高里德伯态间的振子强度,与CA方法得到的结果很接近。计算结果表明,上述振于强度满足某种标度律。 关键词：     

Calculation and extrapolation of oscillator strengths in Rb-like,multiply charged ions

The oscillator strengths of dipole transitions between energy levels of the lowest configurations of ions of the Rb I isoelectronic sequence with nuclear charge Z=41–46 are calculated on the basis of the model potential method using an energy approach. For certain ions the reported data are published here for the first time. It is shown that the contribution of core polarization to the oscillator strength attains 15% for some transitions.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 89–92, January, 1996.     

Study of Rydberg transitions in NaHe

Einstein coefficients and oscillator strengths for electronic transitions in the Rydberg radical NaHe have been calculated with the molecular-adapted quantum defect orbital (MQDO) method. The correctness of our estimations has been established on the basis of their good agreement with the results of a reliable complex calculation available in the literature. Transition probability data involving Rydberg states lying higher in energy than those so far reported are supplied.     

Electric dipole transitions for La I (Z=57)

Wavelengths, weighted oscillator strengths and transition probabilities for electric dipole (E1) transitions for some excited levels in neutral lanthanum (La I, Z=57) have been calculated using the multiconfiguration Hartree-Fock (MCHF) method within the framework of Breit-Pauli relativistic corrections. Results obtained have been compared with other calculations and experiments. A discussion of these calculations for La I in this study has also been given in view of the MCHF method.     

Optimisation of the dipole-Coulomb approximation for high-l Rydberg states of polar molecules

ABSTRACT

The present work deals with the question of the origin choice to get the maximal accuracy of the dipole-Coulomb approximation in the theory of molecular Rydberg states with high orbital momentum l. Concerning birefringence in polar molecules, the question of adequate origin choice has first been raised in the classical work by Buckingham & Longuet-Higgins in 1968, where it has been taken into account that the dipole moment of a polar molecular core (cation) depends on the origin choice. This dependence also leads to inseparability of dipole and quadrupole corrections to the Rydberg electron spectra in polar molecules. In the present work a new option for the problem is proposed as applied to the dipole-Coulomb approximation. Considering a simplified model of a molecular core as a system of N effective fixed point charges, we show both analytically and numerically that the optimal choice of origin, at least for a linear core, is the geometric centre of the core. On the other hand, results of the present work as well as previous publications show that the problem raised by Buckingham and Longuet-Higgins does not have a universal solution.

Abbreviations: RS: Rydberg state; RSs: Rydberg states; ZEKE: zero electron kinetic energy; MATI: mass-analysed threshold ionisation; QDT: quantum defect theory; DCA: dipole-Couloumb approximation; CD: centre of dipole; CC: centre of charge; GC: geometric centre; DCAGC: dipole-Couloumb approximation with origin in the geometric centre; DCACD: dipole-Couloumb approximation with origin in the centre of dipole