Analyse von Hyperfeinstrukturen des Eu151, Am241 und einiger 3 d-Elemente mittels „Exchange Polarization“

It is shown how several discrepancies in the optical hfs of the Eu can be understood as consequences of the exchange polarization of the inner and outers-electrons by the spin of the half filled (4f ⁷)-subshell, an effect which should produce additional magnetic fields at the nucleus. Thus from the two different values of the electronic splitting constanta _6s in the two Eu-II ground states the polarization field from the 6s-shell (Δ H _6s ) is determined to be ca. +260 KG, and the formal splitting constantσ (??3 mK) of the (4f ⁷)-subshell yields ca. ?350 KG for the fieldΔ H _(1?5) from the five innern s-shells (n=1?5) in good agreement with the strength of the inner field obtained from recent Mössbauer effect studies.Δ H _(1?5) is deduced to be approximately equal in all sufficiently analysed ground and excited configurations of the neutral and ionised Eu atom ((4f ⁷) 6s, 6p, 5d, 6s ² and 6s 6p). Other elements with half filled subshells (Am, Mn) show similar features in their optical hfs. For Am⁺ ((5f ⁷) 7s) ca. ?2200 KG are found for the inner field (Δ H _(1?6)). For several 3d-elements it was found that the agreement between the calculated polarization fields and those following from experimental results is better than assumed so far.     

Das Kernquadrupolmoment des Mn55

With a recording photoelectric Fabry-Perot spectrometer and an atomic-beam light source the hyperfine structure of the Mn I-resonance linesλ=4031 Å,λ=4033 Å,λ=4034 Å (3d ⁵4s ² a ⁶ S _5/2?3d ⁵4s4p z ⁶ P _7/2,5/2,3/2 ⁰)and of the inter-combination linesλ=5395 Å andλ=5433 Å (3d ⁵4s ² a ⁶ S _5/2?3d ⁵4s4p z ⁸ P _7/2,5/2 ⁰) was measured. Furthermore the resonance lines have been measured with a pulsed atomic-beam in absorption. In this case the quotient (I ₀(ν)?I(ν))/I ₀(ν) was recorded, whereI(ν)=I ₀(ν) exp(?α(ν)d) is the observed intensity with absorption andI ₀(ν) the intensity of the light source. From the hyperfine structure splitting the value of the electric quadrupole moment of Mn⁵⁵ was derived to be:Q(Mn⁵⁵)=+(0.35±0.05)·10^?24 cm².     

Energy levels of ions of silver and rhodium isoelectronic sequences with <Emphasis Type="Italic">Z</Emphasis> < 86

The method of extrapolation of the parameter of a model potential for states of one electron (4f, 5s, 5p, 5d, 5f) above the core 1s ²2s ²2p ⁶3s ²3p ⁶3d ¹⁰4s ²4p ⁶4d ¹⁰ and one vacancy (4d ⁹) in the same core is applied to calculate the energy levels in the silver and rhodium isoelectronic sequences with the maximum nuclear charge Z = 86. The energy levels of Ag-and Rh-like ions were used for the calculation of the energies of resonance transitions to the ground state ¹ S ₀ in Pd-like ions. Good agreement between the theoretical and calculated energies of the resonance transitions in Pd-like ions indicates the reliability of the results obtained.     

The Fokker-Planck equation for quantum noise of theN-level system

The hyperfine structure of the ReI-lines λκ 4889 å (5d⁵ 6s 6pz ⁸P_7/2?5d⁵ 6s² a ⁶S_5/2) and 5275 å (5d⁵ 6s 6p z⁸P_5/2?5d⁵ 6s² a⁶S_5/2) was measured by a photoelectric recording double Fabry Perot spectrometer using enriched isotopes of Re¹⁸⁵ and Re¹⁸⁷, which have been excited in liquid air cooled hollow cathodes. Besides the usual recording the signal was also measured by a digital voltmeter and punched into paper tape making it possible to evaluate the measurements by a computer. The linewidth obtained in the experiments was small enough that besides the splitting of the⁸P states also the splitting of the ground state could be detected in asymmetries of the hyperfine structure components. By the mathematical analysis of the components it was possible to derive the quadrupole coupling constantB of the 5d⁵ 6s² a ⁶S_5/2 ground state: 5=1.6(8)· 10^?3cm^?1 for Re¹⁸⁵ and Re¹⁸⁷. The quadrupole moments of Re¹⁸⁵ and Re¹⁸⁷ have been estimated fromB (z⁸P_{7/2, 5/2}) with LS coupling eigenfunctions considering relativistic effects: Q(Re¹⁸⁵)=2.30 (4) [90] · 10^?24 cm² Q (Re¹⁸⁷)=2.20 (4) [90] · 10^?24 cm². (Figures in round brackets are experimental errors, those in square brackets are estimated uncertainties introduced by the theoretical evaluation.) Using these results and the knownB (a ⁶S_5/2) of Re¹⁸⁶ and Re¹⁸⁸ also the nuclear quadrupole moments of these isotopes were derived. Q(Re¹⁸⁶)≈Q(Re¹⁸⁸)≈0.4 · 10^?24 cm².     

Gleichzeitige Messung von Hyperfeinstruktur,Starkeffekt und Zeemaneffekt des85Rb19F mit einer Molekülstrahl-Resonanzapparatur

A molecular beam resonance apparatus with electric quadrupole lenses asA- andB-fields and with superimposed parallel electric and magnetic transition-fields was used. Molecules in different rotational statesJ, m _J are separated by theA-field. Spectra of molecules in different vibrational states are resolved by their different Starkeffect energies. By this means the following electric and magnetic properties of the molecule could be measured in the rotational stateJ=1 and vibrational statesv=0 and 1: The magnetic and electric dipole moment of the molecule, the scalar and the tensor nuclear dipole — dipole interactiond _s andd _T, the nuclear spinrotational interactionc _F andc _Rb, the nuclear quadrupole interactioneqQ, the nuclear magnetic moment μ_Rb, the anisotropy of the diamagnetic susceptibility ξ_⊥?ξ_∥, the anisotropy of the diamagnetic shielding of the external field by the electrons at the position of the nuclei σ_⊥?σ_∥. Using these quantities it was possible to calculate the quadrupole moment and a weighted quadrupole moment of the electronic charge distribution. The results are: (J=1,v=0) μ_el=8,5464 (17) debμ _J/J=?29,79(2)x10^?6 μ _B d _s/h=0,36(23) kHzd _T/h=0,69(22)kHzc _F/h=10,42(70) kHzc _Rb/h=0,479 (48) kHz.eqQ _Rb/h=?70,3410(26) MHzμ(1?σ_S)Rb=1,3474(5) μ_k (ξ⊥-ξ _∥)=12(6)×10^?30 erg/Gauß² (σ_⊥-σ∥)_Rb=?3,8(2,1)×10^?4 (σ⊥-σ _∥)_F=?2,6(3)×10^?4     

X-ray photoelectron spectroscopy of FeP phosphide

The structure of the outer and inner electron spectra of iron (2p, 3p, 3s, and 3d) and phosphorus (3s and 3p) atoms in FeP monophosphide is studied in detail by the X-ray photoelectron spectroscopy (XPS) method. On the basis of the analysis of the binding energy of electrons, as well as the parameters characterizing the structure of experimental spectra, a conclusion is made that Fe³⁺ (d ⁵) cations in FeP are stabilized in a state with intermediate value of the total spin (IS, S = 3/2). The range of values of intra-atomic parameters (10Dq, J _H ) is established in which the consideration of the high degree of covalence of Fe–P bonds may lead to the stabilization of (FeP₆)^15– clusters in the IS state.     

Configuration interaction and radiative constants in spectra of argon-like Sc IV-Fe IX ions

The probabilities of the 3p ⁵3d, 3p ⁵4s?3p ⁶, 3p ⁵4p, 3s3p ⁶3d electric dipole transitions and radiative lifetimes of the 3p ⁵3d, 3p ⁵4p, 3p ⁵4s, and 3s3p ⁶3d levels are calculated for the Sc IV–Fe IX isoelectronic sequence.     

Manifestation of the Coster-Kronig effect in the near-threshold electron-impact excitation of the Cd<Superscript>+</Superscript> ion

The near-threshold portions of the energy dependences of the effective excitation cross sections of the resonance transition 4d¹⁰5p²P_1/2° → 4d¹⁰5s²S_1/2 and the two-electron forbidden transition 4d⁹5s²²D_5/2 → 4d¹⁰5p²P_3/2° in the spectrum of the Cd⁺ ion were investigated by the spectroscopic method in crossed electron and ion beams. In the region of energy splitting of the ²P° and ²D levels, a significant resonance contribution of the autoionizing states of cadmium (decaying during the Coster-Kronig process) to the effective excitation cross sections of the noted transitions was revealed for the first time. It is found that the resonance contribution manifests itself much more strongly for the forbidden transition in comparison with the more intense resonance transition; i.e., the manifestation of the Coster-Kronig effect in the electron excitation of ions depends strongly on the cross section of the direct process. It is ascertained that, during the Coster-Kronig process, the main contribution to the resonance excitation of both the resonance and the two-electron forbidden spectral transitions is from the low-lying terms of the series of autoionizing states 4d¹⁰5p(²P_3/2°)ns, md and 4d⁹(²D_3/2)5s²ns, md, which are in the splitting region of the ²P_{1/2, 3/2}° and ²D_{5/2, 3/2} levels, rather than from the high-lying atomic autoionizing states of cadmium, which are located near the ionization limits (corresponding to the and ²P_3/2° and ²D_3/2 levels).     

Observation of high efficiency of Raman scattering in the process of the three-photon ionization of samarium atom

Very high efficiency of Raman scattering on samarium atoms in the process of three-photon ionization has been detected. An intense maximum attributed to the one-photon transition 4f ⁶5d6s ⁹ H ₂ → 4f ⁵5d6s ^{2 7} D ₃° between two excited states is observed in the dependence of the yield of Sm⁺ ions on the laser-radiation frequency. The 4f ⁶5d6s ⁹ H ₂ state is populated owing to the spontaneous Raman scattering 4f ⁶6s ^{2 7} F ₃ + ω ? ν → 4f ⁶5d6s ⁹ H ₂.     

Hyperfine magnetic anomaly in isotopic pairs <Superscript>151, 152</Superscript>Eu and <Superscript>152, 153</Superscript>Eu

High-resolution laser spectroscopy measurements of optical hyperfine splitting on the ^{151, 152, 153}Eu isotopes were performed on the atomic transition 4f ⁷6s ^{2 8} S _7/2 → 4f ⁷6s6p ⁶ P _5/2 at λ ≈ 564.58 nm. Values of the nuclear magnetic dipole and electric quadrupole moments are obtained from the measured hyperfine splitting and the magnetic hyperfine anomalies in the isotope pairs ^{151, 152}Eu and ^{152, 153}Eu are deduced. The absolute values of the hyperfine anomaly in both cases are unusually large: 5 (1)%. The possible sources causing these anomalies are discussed.     

The probabilities of radiative transitions and lifetimes of levels in the spectra of Cu XX,La IV

The probabilities of radiative electric dipole transitions 2p ⁵3p, 2p ⁶–2p ⁵3s, and 2p ⁵3d in the spectrum of neon-like copper Cu XX and 5p ⁵6p, 5p ⁶–5p ⁵6s, 5p ⁵7s, and 5p ⁵5d in the spectrum of xenon-like lanthanum La IV are calculated. The wave functions of the intermediate coupling were found from the wellknown experimental energy levels by the least-squares method (LSM). To transfer to an absolute scale the radial integrals for the transitions calculated in the form of a length on the Hartree–Fock functions have been used. By summing the calculated probabilities of the transitions, the lifetimes of the levels of configurations 2p ⁵3s, 2p ⁵3p, and 2p ⁵3d in the spectrum of Cu XX and levels of configurations 5p ⁵6s, 5p ⁵6p, and 5p ⁵7s in the spectrum of La IV have been obtained.     

New magic nuclei and conditions of their formation

The systematic studies of the arrangement features of single-particle nucleon subshells in even-even ^90,92,94,96Zr isotopes and behavior of some known “magicity parameters” in isotopes and isotones neighboring the ⁹⁶Zr nucleus have led to the interpretation of ⁹⁶Zr as a new doubly magic nucleus. Analysis of the structure of nucleon shells in the ⁹⁶Zr nucleus revealed a feature, which consisted in that near the Fermi energy it had filled proton (π1f _5/2) and neutron (v2d _5/2) subshells with an identical and large total momentum j = 5/2, which was called the j-j coupling. Above the π1f _5/2 shell, there is another filled shell (π2p _1/2) with two j = 1/2 protons. Applied to other filled shells, this empirical rule allowed revealing several new nontraditional magic nuclei: ⁹⁶Sr (Z = 38, N = 58), π1f _5/2, v2d _5/2, and v3s _1/2 subshells; ⁵⁴Ca (Z = 20, N = 34), π2p _3/2, v1d _3/2, and v2p _1/2 subshells; a pair of ³⁰Si (Z = 14, N = 16) and ³⁰S (Z = 16, N = 14) nuclei, π1d _5/2, v1d _5/2, and (π/v)2s _1/2 subshells; and a pair of ¹⁴C (Z = 6, N = 8) and ¹⁴O (Z = 8, N = 6) nuclei, 1p _3/2, v1p _3/2, and v2p _1/2 subshells. The existence of the magic nuclei ^52,54Ca is widely discussed in the literature, the possibility of the existence of the other nuclei found is confirmed by the systematics of the behavior of the “magicity” parameters. The fact that shells with some nucleon numbers different from the classical magic numbers are closed may be due to the manifestation of a new type of interaction between nuclear protons and neutrons occupying certain subshells.     

Bestimmung der Hyperfeinstrukturaufspaltungen der Scandium-Grundzustände2 D 3/2 und2 D 5/2 und des Quadrupolmomentes des Sc45-Kernes

The hyperfine structure splittings of the electronic ground states² D _3/2 and² D _3/2 of the stable isotope Sc⁴⁵ have been measured by the atomic beam magnetic resonance method. From these splittings the magnetic dipole and electric quadrupole interaction constants are found to bea _3/2=(269,560±0,02) Mc/sb _3/2=?(26,37±0,1) Mc/sa _5/2=(109,034±0,01) Mc/sb _5/2=?(37,31±0,1) Mc/s. The values of the electric quadrupole moment calculated fromb _3/2 andb _5/2 differ by about 5% indicating that the configuration 3d 4s ² of the ground states is perturbed by higher configurations. Averaging these two values we obtain for the quadrupole moment of Sc⁴⁵ Q(Sc⁴⁵)=?(0,22±0,01) · 10^?24 cm².     

Das Vorzeichen der Hyperfeinstruktur-Aufspaltung des 3d 5 4s 2 6 S 5/2-Grundzustandes des Mn55

Using a double Fabry-Perot interferometer and an atomic-beam light source, the sign of the hyperfine-structure splitting of the 3d ⁵ 4s ^{2 6} S _5/2 ground state of Mn⁵⁵ has been determined to be negative. The absolute value of the splitting previously has been measured byWoodgate andMartin.     

Zur Frage des Grundzustandes im Tb I-Spektrum

Analysis of the optical spectrum of Tb I confirms the conclusion reached byBender, Penselin andSchlüpmann from atomic beam magnetic resonance observations, that the lowest multiplet in the 4f ⁸5d6s ² configuration is⁸ G. The lowest level, however, is not⁸ G _15/2, but⁸ G _13/2, which is the true ground level of the Tb atom, provided the determination of the relative position of 4f ⁹6s ^{2 6} H _15/2 with respect to 4f ⁸5d6s ^{2 8} G _15/2 byBender c. s. is correct.     

Excitation of even levels of erbium atoms without a change in the number of 4<Emphasis Type="Italic">f</Emphasis> electrons

The excitation of even levels of erbium atoms by slow electrons that occurs without a change in the number of electrons in the 4f shell is experimentally studied. The levels investigated belong to the 4f ¹²6s7s, 4f ¹²5d6s, 4f ¹²6s6d configurations. The cross sections measured at an electron energy of 30 eV lie within the range (0.2–18) × 10^?18 cm².     

Effect of spin crossovers on the Mott-Hubbard transition at high pressures

The effect of spin crossovers in d _n terms on the effective Hubbard parameter (U _eff) determining the gap between the lower and upper Hubbard bands is analyzed using a many-electron approach to describe the electron structure of Mott insulators. A new mechanism of the insulator-metal transition is established for d ⁵ ions, which is related to a decrease in U _eff caused by spin crossover. For other ions, the U _eff value is either independent of pressure (d ², d ⁴, d ⁷) or it exhibits nonmonotonic growth (d ³, d ⁶, d ⁸).     

Determination of electronic ground state properties of a dinuclear iron(II) spin crossover complex

The dinuclear complex [(Fe(L-N₄Me₂))₂(BiBzIm)](ClO₄)₂?2EtCN (1) has been investigated by Mössbauer spectroscopy carried out in the temperature range from 5 to 150 K with externally applied magnetic fields of up to B = 5 T. By means of a consistent simulation of all experimental data sets within the Spin Hamiltonian formalism, the zero-field splitting D and the rhombicity parameter E/D of the ferrous high-spin (HS) site in this complex was determined to be D = ?15.0 ± 1.0 cm^?1 and E/D = 0.33 respectively. The sign of the quadrupole splitting of the HS site is positive which indicates that this iron site of the dinuclear complex 1 has an electronic ground state with the d_xy orbital being twofold occupied.     

Spontaneous Raman scattering upon resonant three-photon ionization of a samarium atom

The manifestation of spontaneous Raman scattering upon the three-photon ionization of a samarium atom has been investigated. The dependence of the Sm⁺ yield on the laser frequency, along with the peaks due to the two-photon excitation of bound states from different levels of the 4f ⁶6s ^{2 7} F ground term, exhibits a strong peak due to single-photon excitation of the 4f ⁵5d6s ^{2 7} D°₃ state from the 4f ⁶5d6s ⁹ H ₂ excited state. The 4f ⁶5d6s ⁹ H ₂ state was populated as a result of spontaneous Raman scattering. The large amplitude of the observed peak indicates a high efficiency of this process. The estimations performed indicate that the probability of resonant ionization through an excited state populated due to spontaneous Raman scattering can be comparable with the probability of three-photon ionization through the two-photon intermediate resonance. The necessary conditions for implementing this channel of resonant three-photon ionization are formulated.     

Analysis of the spectrum of the Zn-like Kr VII ion: Highly excited 4<Emphasis Type="Italic">p</Emphasis>4<Emphasis Type="Italic">d</Emphasis> and 4<Emphasis Type="Italic">p</Emphasis>5<Emphasis Type="Italic">s</Emphasis> configurations

The spectrum of the Zn-like Kr VII ion, excited in a capillary discharge and recorded with a high resolution in the wavelength range of 300–1000 Å, was studied. Previously performed identification of the transitions from the levels of the 4s4f, 4s5s, 4s5p, and 4s5d configurations is confirmed and extended, and the energies of these levels are specified. The (4p ²+4s4d)?4p4d and (4p ²+4s5s)?4p5s transitions are identified for the first time, and the energies of all the levels of the 4p4d and 4p5s configurations are determined. The results of the analysis performed are confirmed by semiempirical calculations in terms of the Hartree-Fock method. These results are also shown to conform to the experimental data obtained for lighter ions of the Zn I isoelectronic sequence.