Laser photoelectron spectrometry of Sc− and Y−: A determination of the order of electron filling in transition-metal anions

The photoelectron spectra of Sc^? and Y^? have been obtained in a crossed ion- and laser-beam experiment. Analysis of the Sc^? spectrum yields two bound terms of 3d4s² 4p configuration (¹D⁰ and ³D⁰), with EA(Sc) = 0.189 ± 0.020 eV and an excited-state binding energy of 0.042 ± 0.020 eV. Similarly, the (4d5s² 5p) ¹D⁰ ground state of Y^?is bound by 0.308±0.012eV and a (4d5s²5P)³D⁰ excited term is bound by 0.165± 0.025 eV. With the determination of the bound electronic configuration of Sc^? as 3d4s²4p, the order of filling of electron shells of the first transition series negative ions is found to be 4s²4p, 3d4s²4p, followed by 3d^k4s² (k = 3,4,…, 10).     

A test of the absolute Ni(I) gf-value scale by using mean lives of selected levels for the configurations 3d84s4p and 3d94p

Lifetimes for 11 levels of the configurations 3d⁸4s4p and 3d⁹4p in Ni (I) have been measured by the delayed coincidence method, following selective dye-laser excitation in a wavelength range between 299 and 338 nm. The results are compared with earlier laser excitation and Hanle effect lifetime measurements and with lifetimes derived from the gf-values of Huber and Sandeman. Comparisons with the results of Huber and Sandeman show consistently excellent agreement.     

Configuration interaction screening factors for Cu2+ in crystal fields

The effect of configuration interaction by the electrostatically correlated crystal field leads to a screening of the crystal field parameters by a factor (1 + K^(k)). For Cu²⁺, the number of contributing states in the excited 3 d⁸4s and 3d⁸4d configurations is low and numerical estimates using analytical wavefunctions suggests that this effect may not be negligible.     

Spectra and oscillator strengths of 3p63d9--3p53d10 and 3p63d9--3p63d84p transitions for cobalt-like Sn23+ ion

This paper calculates the spectra and oscillator strengths for highly ionized cobalt-like Sn23+ ions 3p63d9 3p53d10,3p63d9 3p63d84p transitions by using a multi-configuration self-consistent field method program together with the proposed fitting formula.The calculations have a good agreement with observations.     

Oscillator strengths for 3dn4s → 3dn4p transitions in the iron series

The observed oscillator strengths for the 3dⁿ4s → 3dⁿ4p transitions in the iron series show anomalous behaviour for Cr and Mn : the former is exceedingly small whereas the latter is unusually large.Theoretical Hartree-Fock gf-values are reported and a considerable discrepancy with experimental values is noted for Cr. The effect of the interaction of 3dⁿ4p with 3d^n?14s4p is studied using a fixed core, multi-configuration Hartree-Fock approximation. This interaction does not improve significantly the agreement with observed values.     

Configuration mixing and crystal-field splitting of Cr2+ in CdS

The effect of interaction of excited configurations 3d³4s, 3d³4p and 3d³4d with the ground 3d⁴ configuration on the crystal field splitting (E- T₂) of the tetrahedral Cr²⁺ ion in CdS has been studied by a rigorous method in which the energy matrix constructed in a basis of states belonging to both the ground and excited configurations has been directly diagonalised. Such a fairly rigorous treatment yield surprising results and interesting conclusions. Even though the calculation is based on an ionic model of the crystal field, it is found that inclusion of excited configurations accounts for the entire crystal field splitting observed experimentally in this particular case of Cr²⁺ in CdS. The configuration mixing in our treatment yields for the crystal field splitting a result few times greater than that found when the calculation is confined within the ground configuration only. Furthermore, the present investigation indicates that the second order perturbation method used in the earlier treatment was quite inadequate in the case of Cr²⁺ in CdS.     

Oscillator strengths for selected 3dn4s−3dn4p transitions of the iron-group elements

Absolute transition probabilities are calculated for selected 3dⁿ4s?3dⁿ4p transitions of the iron-group elements; configuration interaction effevts are taken into account. Comparisons with Hartree-Fock and multi-configuration Hartree-Fock results and with experimental data show that the scaled Thomas-Fermi method for calculation radial wave functions is useful procedure.     

Paramagnetic Ru5+ and Ru3+ centers in TiO2:Ru

Paramagnetic resonance on TiO₂ single crystals doped with ruthenium have shown the presence of both Ru⁵⁺(4d³) and Ru³⁺(4d⁵) in oxygen octahedral coordination.     

Oscillator strengths for the 2s2, 2p2, 2s3s(1S)-2s2p(1P) transitions of B(II)

Accurate configuration interaction wavefunctions for the 2s²(¹S), 2p²(¹S), 2s3s(¹S) and 2s2p (¹P) states of B(II) are calculated in a single optimized orbital basis of 7s, 6p and 4d Slater-type orbitals. 95, 84, 57 and 90% of the correlation energies, respectively, are realized by these wavefunctions. Oscillator strengths for the three ¹S-¹P transitions are calculated from these and from less accurate wavefunctions in the same orbital basis. The length values obtained from our most accurate wavefunctions, in order of increasing ¹S energy, are 0.9885, 0.202 and 0.007. The degree of accuracy of these oscillator strengths is estimated by noting the convergence to final values as increasing percentages of correlation energies are included in the wavefunctions together with the increasing agreement between length and velocity formulas. The exact theoretical oscillator strength for the resonant line is projected to be 0.985 with an error almost certainly not greater than ±0.015. The theoretical oscillator strengths for the other lines are considered to be 0.21±0.02 and less than 0.007, respectively.     

Vibrational and electronic spectra of alkali halides doped with CrO42− ions

The i.r. spectra of alkali halides doped with FrO₄^2? ions are very sensitive to the concentration of background divalent impurities. Highly pure crystals containing CrO₄^2? ions show a 5 line i.r. spectrum in the v₃ stretch frequency region. One of these lines is attributed to CrO₄^2? ions in perfect crystal surroundings having T_d symmetry and the other 4 lines are attributed to C_s symmetry produced by a charge compensating anion vacancy in the nearest neighbour position. If the crystal contains a concentration of divalent cation impurity which is equal to or more than that of CrO₄^2? ions, a different spectrum characteristic of C_2x symmetry as well as the line corresponding to T_d symmetry are obtained. The crystals of ordinary purity contain all the three (C_s, C_2x and T_d symmetry) species and show eight line spectra. The changes in force constants calculated from the observed splitting of the energy levels agree with those evaluated from the known polarizability of the chromate ions.At 600°C, the vibration spectra of the highly pure crystals doped with CrO₄^2? ions show an increase in intensity of the line characteristic of T_d symmetry and the other lines practically disappear, because the anion vacancies move away from the neighbourhood of the CrO₄^2? ions at high temperatures. The energy of association of the vacancy with CrO₄^2? ions and the energy of migration of the vacancy are derived from the spectra obtained at different temperatures and with different heat treatments.The electronic spectra of the crystals show 3 bands (at 345, 270 and 240 nm for KCI). The lowest energy band has a fine structure with a spacing of about 800 cm^?1 at LAT. Since the transition involved is from a non-bonding to an antibonding state, the Condon parabola is shifted in the excited state and therefore the fine structure is attributed to a vibrational progression involving a totally symmetric frequency 800 cm^?1 in the excited state.     

The 3d photoabsorption of Tm3+

The four lines predicted theoretically in Tm³⁺ 3d photoabsorption are observed. By fitting the eigenvalues and the observed energies, new values of radial parameters are determined and it is shown that the configuration 3d⁹4f¹³ in Tm³⁺ is better described in j-j coupling.     

C42+的几何构型和Jahn Teller效应

用从头计算法QCISD/6-311G得到了C₄²⁺分子的10种不同的几何构型,其中包括C_s,C_∞v,C_2v,D_2h,D_∞h,D_4h,D_2d,C_3v等不同的构型.计算表明C₄²⁺的T_d构型不能稳定存在,详细讨论了T_{d 关键词： 几何构型 4}²⁺')" href="#">C₄²⁺ Jahn Teller效应     

Covalent distribution of spin in V2O3:O17 nuclear resonance

O¹⁷ nuclear magnetic resonance has been observed in metallic V₂O₃ with frequency shifts from (?0.10 ± 0.02)-(?0.05 ± 0.02) per cent between 170 and 460°K respectively, a linewidth of 37 ± 5 oe and spin-lattice relaxation rate 1/T₁ ≈ 60 sec^?1 at 296°K. From these quantities, covalency parameters f_s/2S = ? 0.35 × 10^?3 and ?_π/2S ≈ ? 0.07 are calculated. One of the two vanadium 3d electrons in the antiferromagnetic state below the 170°K metal-insulator transition is inferred to lie in a non-magnetic state, while covalent charge transfer augments the spin moment of the other 3d electron to the observed 1.2 μ_B.     

Lifetime of levels belonging to the 3p54p configuration of Ar(I)

The lifetimes of nine levels of Ar(I) belonging to the 3p⁵4p configuration have been measured by the delayed coincidence method, with errors in the range from 4 to 7%. The results are compared with other experimental values and with theoretical calculations using jK coupling and intermediate coupling. From cascade components of the 4p levels, decay lifetime values for some levels belonging to the 3p⁵3d and 3p⁵5s configurations have been inferred.     

Production of muon pairs in the continuum region by 39.5 GeV/cπ±, K±, p and p beams incident on a copper target

General features of the inclusive hadroproduction of muon pairs of mass greater than 1.5 GeV/c² are shown. For incident π^?, the data extend up to M=5.7 GeV/c² (i.e.M²/s≈0.4). The scaling cross section M³dσ/dM for π^?N reactions is much flatter than that for pN reactions and exceeds the latter by two to three orders of magnitude at large M²/s.     

K0 production in e+e− annihilations at 30 GeV center of mass energy

Inclusive K⁰-production has been measured in e⁺e^- annihilation at a center of mass energy of about W = 30 GeV. The ratio of K⁰ + K⁰ production to μ⁺μ^- production is R_K0 = 5.6 ± 1.1 (statist. error) ± 0.8 (system.error) This value is about a factor of three higher than R_K0 at W = 7 GeV. The cross sections (s/β) dσ/dx is consistent with a scaling behaviour.     

Pressure dependent optical absorption edge shift and compressibility of CdCr2Se4 single crystals

The pressure shift of the optical absorption edge (dE_g/dp = (1.1 ± 0.1) × 10^?6 eV bar^?1) and the compressibility (κ = (1.3 ± 0.) × 10^?6 bar^?1) of single crystalline CdCr₂Se₄ have been measured at ambient temperature. These data suggest an interpretation of the fundamental absorption in terms of either p → p interband or p → localized d charge transfer transitions, but exclude excitations involving s-band states.     

The electronic structure of CuCl: An “ab initio” Hartree-Fock SCF-MO study of the CuCl43− cluster

Results from restricted Hartree-Fock SCF-MO calculations on the CuCl₄^3? cluster occurring in solid CuCl are reported. The chemical bonding is discussed on the basis of a population analysis of the ground state orbitals. Calculations on the first ionized states show the Cu 3d electrons to be less tightly bound than the Cl 3p electrons in contrast to Koopmans' theorem predictions and in agreement with experiment. The high degree of localization of the 3d hole orbitals obtained is in conflict with earlier estimates of d-bond covalency. It is suggested that the “Ham effect” rather than covalency is responsible for the reduced spin orbit splitting that can be deduced from the observed exciton absorption. The potential surface for a Cu⁺ ion moving in the field of neighbouring Cl^? ions, has been determined from calculations on the CuCl₄^3? cluster in which the metal ion has been displaced towards a face, an edge or a vertex of the surrounding tetrahedron. The vibration frequency and the activation energy for the diffusion of Cu⁺ ions obtained are in fair agreement with the experimental data. These results support the viewpoint that the anomalous change in scattering intensity with temperature observed in X-ray and neutron diffraction studies is due to the presence of a substantial fraction of the Cu⁺ ions on interstitial lattice sites.     

Nature of optical properties of GdFe3(BO3)4 and GdFe2.1Ga0.9(BO3)4 crystals and other 3d5 antiferromagnets

Influence of the partial substitution of paramagnetic Fe³⁺ ions by diamagnetic Ga³⁺ ions in the trigonal crystal GdFe₃ (BO₃)₄ on its optical and magnetic properties is studied and discussed in connection with problems common for all antiferromagnets containing 3d ⁵ ions. Polarized optical absorption spectra and linear birefringence of GdFe₃ (BO₃)₄ and GdFe_2.1Ga_0.9 (BO₃)₄ single crystals have been measured in the temperature range 85–293 K. Specific heat temperature dependence (2–300 K) and structure of GdFe_2.1Ga_0.9 (BO₃)₄ crystal have been also studied. As a result of substitution of 30% Fe to Ga the Neel temperature diminishes from 38 till 16 K, the strong absorption band edge shifts on 860 cm^-1 (0.11 eV) to higher energy and the d-d transitions intensity decreases substantially larger than the Fe concentration does. Strong absorption band edge is shown to be due to Mott-Hubbard transitions. Correlation between position of the strong absorption band edge and the Neel temperature of antiferromagnets has been revealed. Properties of the doubly forbidden d-d transitions in the studied crystals and in other antiferromagnets are explained within the framework of the model of the exchange-vibronic pair absorption, which is theoretically analyzed in detail. The model permitted us to determine the connection between parameters of d-d absorption bands (intensity, width and their temperature dependences), on the one hand, and the exchange, spin-orbit and electron-lattice interactions, on the other hand.     

Crystal field splitting of 5d states in Ce3+:YPO4

The superposition model is used to obtain a new identification of the 5d levels in Ce³⁺: YPO₄, resulting in a revised parametrization of the 5d crystal field. Electrostatic and pseudo-potential models are employed to relate these parameters to those obtained from 4f crystal field splittings.