Fundamental absorption spectra of transition metal chlorides

The optical absorption spectra of MnCl₂, FeCl₂, CoCl₂, and NiCl₂ have been measured over the energy range from 2 to 30 eV. The gross features of the spectra, especially broad bands above 10eV, are alike in all of the four materials. The charge transfer bands due to the electronic transitions from the 3p level of chlorine to the 3d and 4s levels of metal ions and the band due to the 3d → 4s transition are assigned in the spectra.     

X-ray absorption near edge structure in some Mn compounds

The shapes of the manganese K-absorption edge in the compounds MnSO₄H₂O, MnF₂, MnCO₃, MnO and MnS have been studied using a Cauchois type X-ray spectrograph. Three peaks A, B and C observed in the main edges have been assigned the electronic transitions ls → 3d, ls → 4s and ls → 4p respectively. The transitions have been explained on the basis of the Z + 1 analogy. It has also been shown that the 3d → 4s and 4s → 4p orbital separations depend on the partial charge of an ion in its compound.     

Rate processes on fractals: Theory,simulations, and experiments

Heterogeneous kinetics are shown to differ drastically from homogeneous kinetics. For the elementary reaction A + A products we show that the diffusion-limited reaction rate is proportional tot ^– h[A]² or to [A]^x, whereh=1- d _s/2, X=1+2/d _s =(h-2)(h-1), andd _s is the effective spectral dimension. We note that ford = d _s =1, h =1/2 andX = 3, for percolating clustersd _s = 4/3,h = 1/3 andX = 5/2, while for dust ds <1, 1 >h > 1/2 and >X > 3. Scaling arguments, supercomputer simulations and experiments give a consistent picture. The interplay of energetic and geometric heterogeneity results in fractal-like kinetics and is relevant to excitation fusion experiments in porous membranes, films, and polymeric glasses. However, in isotopic mixed crystals, the geometric fractal nature (percolation clusters) dominates.     

Untersuchungen zum Stark-Effekt metastabiler Terme im Ba I-Spektrum durch Nachweis von Hochfrequenzübergängen

By detection of r.f.-transitions between Zeeman-sublevels the Zeeman-splitting of the metastable 6s 5d-levels and of the 6s 6p³ P ₁-level of the even Ba-isotopes was investigated under the influence of an electric field in addition to a magnetic field. From the measurements the following tensor polarizabilities were deduced: α_ten(³D₃)=?29(5) kHz/(kV/cm)², α_ten(³ D ₂)=?13(3) kHz/(kV/cm)², α_ten(³D₁)=?10(2) kHz/(kV/cm)², α_ten(¹ D ₂)=?16(3) kHz/(kV/cm)². No effect due to electric fields up to 50 kV/cm was observed in the Zeeman-splitting of the 6s 6p ³ P ₁-level. Therefore the tensor polarizability of the 6s 6p³P₁-level must be much smaller than those of the 6s 5d-levels. The results will be discussed by considering the oscillator strengths both of the infrared transitions between the two multiplets 6s 5d ³ D and 6s 6p ³ P and of transitions to other low lying levels.     

Laser spectroscopy of stable Os isotopes

Doppler-free isotope shift measurements of the stable even ^184–192Os and ^187,189Os odd isotopes have been performed for the first time on the 5d ⁶6s ^{2 5}D₄→5d ⁶6s6p ⁷F₄ (305.9 nm) transition in the neutral atom by atomic beam laser spectroscopy and on the ionic 5d ⁶6s ⁵D_9/2→5d ⁶6p ⁶D_7/2 (228.2 nm) transition by fast collinear ion-laser spectroscopy. The measurements were carried out in Manchester and at the IGISOL facility in Jyväskylä in Finland, respectively. The results presented are the most precise measurements to-date of the absolute isotope shifts.     

Experimentally determined transition probabilities of the systems 6p2→6p6d, 6p7s, 6p8s of neutral lead

Branching ratio measurements have been performed for all of the observed transitions from eight levels in neutral lead (6p²→6p6d, 6p²→ 6p7s, 6p²→6p8s) excited in a hollow cathode discharge in the 200–730 nm spectral range. From the relative emission intensity data, a set of absolute transition probabilities is derived for 28 lines, including lines for which transition probabilities have not been previously published. The absolute scales are obtained by averaging the measured lifetimes of the ³P⁰_1,2, ¹P_1⁰(6p7s), ³F^0_2,3, ³D^0_1,2(6p6d) levels.     

Improved infrared and visible emission spectra of the H3 and D3 molecules

Better-resolved Rydberg-Rydberg emission spectra of the neutral H₃ and D₃ molecules in the infrared and visible regions, with less interference from H₂ and D₂ emission, have been obtained by using a Droege-Engelking type of corona discharge source. Using nl_λ notation, the lower electronic states are 3p₁ in the infrared and 2p₀ in the visible, and the upper electronic states are mixed (3s,3p₀,3d₀,3d₁,3d₂) states. In particular, a line near 16 842 cm⁻¹ in H₃, previously obscured by an H₂ line, reveals a (3s,3d) interaction that is confirmed by other lines. The spectra are analysed including this interaction. However, fits to effective Hamiltonians still have relatively large standard deviations, probably partly due to poor convergence of the rotational expansions and partly due to many small perturbations of the levels by background states.     

Hyperfeinstruktur-Untersuchungen im Rhenium-I-Spektrum

By optical means (i.e. hollow cathode, Fabry-Perot-interferometer and spectrograph) the hyperfine structure of 15 transitions in the Re-I spectrum was investigated. This permits to state the hfs coupling constantsA, B for 15 levels belonging to the configurations (5d ⁵) 6s ², (5d ⁵) 6s 6p, (5d ⁵) 6s 7s, (5d ⁶) 6s, (5d ⁶) 6p and (5d ⁴) 6s ² 6p. It was found that the (5d ⁵) 6s ^{2 6} S _5/2 ground state, too, shows a small hfs. Of its magnetic splitting both size and sign could be determined (A _0,185,187=?2,2±0,4 mK); for a possible quadrupole splitting upper limits were obtained. Estimates of the quadrupole moments resulted inQ _185,187?2,9b. — In the case of two levels (x ⁶ P _7/2 andy ⁶ F _11/2) the hfs analysis raises doubts as to their classification.     

HD structural isotope effect in hydrogen-bonded 2-aminoethanol

The microwave spectra of the d₃ species of intramolecularly hydrogen-bonded 2-aminoethanol (ODCH₂CH₂ND₂) as well as the d₃-O¹⁸, d₃-N¹⁵ and three d₂ isotopic forms have been studied. The r_s O-(D)?N distance of 2.8027(5) Å in the d₃ species is 0.0058(7) Å shorter than the O-(H)?N distance found earlier for the d₀ species (R. E. Penn and R. F. Curl, Jr., J. Chem. Phys.55, 651–658 (1971)). The anomalous r_s structural parameters $\text{r}\text{OH = 1.14}\text{A}\text{?}$ and ∠COH = 103.7°, when corrected for the systematic error caused by the O?N “shrinkage” upon deuteration, become 1.00 Å and 108°, respectively.     

Hydrogen-induced states in VHx and VDx observed by soft X-ray emission spectroscopy

From measurements of soft X-ray emission spectra (V-L₃) of VH_x and VD_x, a gradual change of d-band of V metal with addition of H(D), and an appearance of H(D)-induced states immediately below the d-band, are clearly demonstrated. The states, located at 7 eV below the Fermi energy for all compositions, are interpreted as being bonding states formed by H(D)-1s and V-3d orbitals. No isotope effects were detected within the accuracy of the experiment.     

Tensor polarizabilities of levels of the configurations 4f 13 6s6p and 4f 12 5d6s 2 in thulium I

The level-crossing technique with parallel electric and magnetic fields was used to measure the tensor polarizabilities of six levels of the configuration 4f ¹³ 6s6p + 4f ¹² 5d6s ² in the Tm I-spectrum. Using intermediate coupling wave functions given by Camus and the experimental values of the tensor polarizabilities, the radial integrals for electric dipole transitions from levels of the configuration 4f ¹³6s6p + 4f ¹²5d6s ² to levels of the configuration 4f ¹³ 5d6s + 4f ¹² 6s ²6p have been determined. The results areI(4f ¹³6s6p,4f ¹³5d6s)=1.98(45)ea ₀ andI(4f ¹²5d6s ²,4f ¹²6s ²6p) = 0.88(25)ea ₀. A comparison between the experimental and the calculated values of the tensor polarizabilities shows an excellent agreement, provided that these radial integrals and the radial integrals for the electric dipole transitions to the ground state configuration 4f ¹³6s ² as determined by Wallenstein from lifetime measurements are used in the calculation, instead of radial integrals computed by Camus with Hartree-Fock wave functions.     

An investigation of unitarity at ISR energies

We analyse the unitarity equation in impact-parameter space using recent ISR data (at s=930 GeV²) on σ_T, dσ/dt (elastic) and d²σ/dtdM² (diffractive) as input. The assumption of s-channel helicity conservation for the diffractive process leads to a diffractive overlap function which is central. Unitarity then restricts single diffraction to satisfy 2σ_d?5.8 mb. The assumption of t-channel helicity conservation, on the other hand, gives the interesting result that diffractive processes are peripheral in b-space if the diffractively produced state has high spin. Unitarity in this case gives no significant bound on 2σ_d. For both cases, non-diffractive processes are peripheral.     

Double discontinuities of wide separation in the X-ray absorption spectra of transition elements in highly oxidized compounds

The paper consists of two parts. (1) The author studied the mechanism of the appearance of the double discontinuities of wide separation in the X-ray L₁ absorption spectrum of Mo in MoO₃, which were found in the recent research about the effects of chemical combination on various X-ray absorption limits, and that of Nb in Nb₂O₅. Then he arrived at the conclusion that the discontinuity of the higher energy corresponds to the electronic transition from L₁ to 5p, and that of the lower energy is attributed to that from L₁ to the 4d, 5s state. (2) The author applied the explanation to the double discontinuities which have been observed by many researchers in the K absorption spectra of 3d transition elements in highly oxidized compounds, and showed that these double absorption discontinuities are ascribed to the electronic transitions K?4p and K ? 3d, 4s.     

Accurate core binding energies of ions from Dirac-Fock calculations combined with experimental atomic binding energies

Core binding energies are reported for the singly-charged alkali ions obtained by removing the outer s electron and for the singly-charged halide ions obtained by adding a P_{$\text{3}\text{2}$} electron. The levels studied are Li 1s, Na 1s, K 2p, Rb 3p, Cs 3d, F 1s, Cl 2p, Br 3p and I 3d. The binding energies were obtained by combining DiracF?ock ΔSCF binding-energy shifts between the ions and the corresponding isoelectronic rare gases with experimental rare-gas binding energies, and also by combining the calculated atomīon shifts with experimental atomic binding energies where available. It is shown that the former approach corrects accurately for the correlation energy, which is not included in single-configuration calculations.     

Study of the energy level structure for the isoelectronic series of scandium-like ions

The structure of the energy level system for 39 ions of the scandium isoelectronic sequence is studied on the basis of the relativistic self-consistent field method taking into account the configuration interaction. The Dirac-Fock equations are solved with subsequent diagonalization of the energy matrix. The ground-state ionization potentials are determined for each ion. The energy levels corresponding to the 3d4s ², 3d ²4s, and 3d ₃ configurations are also calculated. The obtained energy values are compared with the experimental data as well as with the results of calculations carried out by other authors.     

Lifetime measurements of lithiumD-states

We report lifetime measurements of the 1s ² 3d ² D, 1s ²4d ² D, and 1s ²2p ² P states of lithium. The results τ=14.5±0.7 ns, τ=31.0±1.0 ns, and τ=27.9±1.0 ns respectively were obtained by time resolved detection of the resonance fluorescence following pulsed laser excitation.     

On the dynamic conductivity for an electron-impurity system

The correlation function formula for the dynamic conductivity of a system of non-interacting electrons in the field of impurities is analyzed in terms of proper connected diagrams. By selecting those diagrams appropriate in the region of weak coupling and low impurity concentration, a set of coupled equations for the energy broadening γ (ω, ε, n_s) and the energy shift Δ(ω, ε, n_s) is derived, where both γ and Δ depend on the frequency ω of a probing field, the energy ε of the electron, and the concentration, n_g, of impurities. With the assumption of a finite range potential, these equations are solved. It is found that γ (ω, n_s) is smaller than that extrapolated value which the conventional expression γ₀ for the low-concentration collision frequency would predict, in the entire region studied, that the difference γ₀-γ becomes appreciable when the ratio of the average time between scatterings, τ_c, to the average duration of a scattering, τ_d, is 100 or less, that γ (ω, n_s) decreases monotonically from its static value γ (0, n_s), and becomes vanishingly small in the region ω≈1/τ_d, and that in the static limit (ω=0), γ=γ₀[1?(2/π) (γ₀τ_d)+…], that the energy shift Δ is positive, and increases from 0 and reach a peak of magnitude γ₀ as ω is raised from 0. By using the γ and Δ obtained, the dynamic conductivity σ(ω, n_s) for degenerated electrons is calculated. The deviation, σ-σ₀, from the conventional expression σ₀=(?i) (n_ee²/M) [ω-iΓ₀]^?1, (n_e]=number density of electrons), for 0°K, is appreciable when the ratio τ_c/τ_d is 100 or less. The field-term correction, which arises from the modification of the scattering due to the probing field, is found to be negligible in the entire region studied.     

Hidden configurations and effective interactions: A comparison of three different ways to construct renormalized hamiltonians for truncated shell-model calculations

We discuss in general some criteria and methods for constructing effective Hamiltonians. Then three different methods are compared for constructing an effective Hamiltonian to be used in nuclear shell-model calculations for A = 17–20, allowing (A-16) active nucleons in the d_5/2, s_1/2 vector space. For all three methods, the aim is to obtain a d_5/2, s_1/2 model which will simulate the results of a given full d_5/2, s_1/2, d_3/2 model. The three methods for finding the effective Hamiltonian are.

1. (a) conventional low-order perturbation theory;

2. (b) a projection technique, in which we construct a Hamiltonian whose eigenvalues excactly match a selected subset of d_5/2, s_1/2, d_3/2 eigenvalues, and whose eigenvectors excatly match the projections of d_5/2, s_1/2, d_3/2 eigenvectors on the d_5/2, s_1/2 space; and

3. (c) least-square fit to selected d_5/2, s_1/2, d_3/2 energies.

For all three methods, we first restrict the effective Hamiltonian to a linear combination of 1-body and 2-body operators. Then for the perturbation and projection techniques, we also calculate the 3-body-operator terms in the effective Hamiltonian.When the effective Hamiltonians are limited to 1-body and 2-body terms, the leastsquare method yields the best overall fit to the low-lying spectrum of d_5/2, s_1/2, d_3/2     

Hyperfine structure of the atomic osmium spectrum: Superposition of configurations and the effect of nucleus volume

The contributions of the superposition of configurations ns ²5d ⁷6s+ns5d ⁷6sn′s+ns5d ⁷6s ² (n=1–5, n′=7–10) to the parameters of the hyperfine structure a _5d ⁰¹ , a _5d ¹² , a _5d ¹⁰ , a _6s ¹⁰ in the spectrum of the osmium atom Os I are calculated. Nonzero contributions are shown to be made only to the parameters a _5d ¹⁰ and a _6s ¹⁰ . This fact justifies the inclusion of the parameter a _5d ¹⁰ in the semiempirical analysis of experimental values of magnetic dipole constants of the hyperfine structure of the 5d ⁷ s configuration in the spectrum of the osmium atom. The effect of nucleus volume on the parameters of the hyperfine structure in the spectra of osmium isotopes ¹⁸⁷Os and ¹⁸⁹Os is estimated.     

Far U.V. absorption spectra of manganese halides between 20 and 67 eV.

The absorption spectra of evaporated thin films of MnF₂, MnCl₂, MnBr₂ have been measured in the energy range 20–67 eV. The onset of the absorption of 3p Mn²⁺ is about 50 eV. At lower energies, the structures may be attributed to transitions from 2s F^-, 4s Br^- and 3d Mn²⁺ levels.