Hyperfine structure in the configurations 4f 13 6s6p and 4f 125d6s 2 of TmI

The laser-atomic-beam spectroscopy has been used to make precise measurements of the hyperfine structure in transitions starting from metastable states of the configuration 4f ¹²5d6s ² in¹⁶⁹TmI. With the resulting experimental magnetic dipole hyperfine constantsA _J andA _J values from former investigations a parametric analysis of the hyperfine structure in the configurations 4f ¹³6s6p and 4f ¹²5d6s ² has been performed using wavefunctions from fine structure calculations. A comparison of theoretical and experimental hyperfine constants allowed a test of the reliability of the wave-functions used. The hyperfine parameters respectively hyperfine radial integrals determined from the analysis were compared with corresponding data from ab initio calculations for the ground configuration in TmI.     

Configuration interaction effect on the hyperfine structure of the levels of the 6s6p 3 configuration in Bi II

The hyperfine structure splittings of the lines: 318.6980 nm, 328.2567 nm, 330.6264 nm, 332.7443 nm, 339.1810 nm, 340.9208 nm, 549.0347 nm, 589.8241 nm, 610.3918 nm were measured and the hyperfine structures of the levels belonging to the configuration 6s6p ³ in Bi II were determined. The influence on the hyperfine structure of the electrostatic configuration interaction between 6s6p ³ and 6s ²6pn'd configurations was discussed.     

Stark effect of hyperfine levels of the configuration 4f 7 (8 S) 6s6p in the europium I spectrum

The quadratic Stark effect in the hyperfine structure of all levels of the configuration 4f ⁷(⁸ S)6s6p in europium I, which can be excited by electric dipole radiation from the ground state, has been investigated by laser-atomic-beam spectroscopy. From the measured shifts and splittings of the hyperfine components the scalar and tensor polarizabilities have been deduced. From the polarizabilities radial integrals for electric dipole radiation were determined by a parametric analysis. With these radial integrals theoretical values of the polarizabilities were calculated.     

Hyperfine structure in the configuration 4f 115d6s 2 of Er I

Hyperfine constants of low lying levels of the configuration 4f ¹¹5d6s ² in Er I have been measured for the only stable odd isotope,¹⁶⁷Er, using high resolution laseratomic-beam spectroscopy. Hyperfine parameters were evaluated from the experimental data using the effective tensor operator formalism. For this purpose eigenfunctions have been determined from an analysis of the fine structure energies of Er I as well as from ab initio multiconfiguration Dirac-Fock calculations. With the latter method also ab initio hyperfine constants for the levels investigated were evaluated. A comparison of calculated fine structure energies, Landég _J -factors and hyperfine constants with the experimental data allowed a test of the reliability of the fine structure and multiconfiguration Dirac-Fock wavefunctions. Effective nuclear electric quadrupole moments for¹⁶⁷Er have been determined from the experimental hyperfine constants using both calculated relativistic electronic radial integrals and hyperfine parameters for the 4f and 5d electrons in the configuration 4f ¹¹5d6s ² in Er I. From a comparison with the nuclear quadrupole moment measured in the mesic atom Sternheimer shielding factors are calculated. Configuration-interaction contributions to the radial integrals 〈r ^?3〉 _nl ⁰¹ of the 4f and 5d electrons have been determined.     

Hyperfine structure investigations in excitedD-states of171Yb and173Yb

The hyperfine structure splittings in the excited 4f ¹⁴6s6d states of¹⁷¹Yb and¹⁷³Yb have been measured. Isotope selection was achieved by stepwise laser excitation of the¹ D ₂ and³ D _{2, 1} states. The³ D ₃ state of¹⁷¹Yb was excited via collisional excitation of an intermediate level. The magnetic and electric hfs coupling constants are given and compared to ab initio values calculated from relativistic self-consistent-field wavefunctions.     

Observation of quadrupole hyperfine structure in the v6 RQ3 (6) transition of 12CH335Cl

Quadrupole hyperfine structure has been observed in the v₆^RQ₃(6) transition of ¹²CH₃³⁵Cl using a stable CO₂ laser oscillating on the 9.4 μm P(26) line. By heterodyning this laser with another which is locked to the 4.3 μm fluorescence dip of the 00⁰1-00⁰ CO₂ transition, an accurate measurement of the hyperfine splittings has been made. The observed spectrum agrees, within experimental error, to the theoretical values evaluated without the need for a vibrational correction to the quadrupole interaction in the excited vibrational state. The hyperfine component closest to the center of the CO₂ P(26) transition is determined to be 5.6 ± 0.1 MHz from the P(26) line center.     

An oxychloride of divalent ytterbium: Yb4OCl6

Lemon-coloured single crystals of the first oxychloride of divalent ytterbium Yb₄OCl₆ are obtained by metallothermic reduction of YbCl₃ (contaminated with YbOCl) with metallic lithium in a sealed tantalum container at 900 and 750 °C. Yb₄OCl₆ crystallizes with the hexagonal system, space group P6₃mc, Z = 2 with a = 913.78(4) pm, c = 688.70(5) pm, c/a = 0.754 and V_m = 149.97(2)cm³mol⁻¹. An important feature of the crystal structure of Yb₄OCl₆ is the O²⁻ centred (Yb²⁺)₄ tetrahedron that is surrounded by 18 Cl⁻ ions. These provide the necessary connections to other [OYb₄] units. The [OYb₄] tetrahedra are, viewed by themselves, arranged in the fashion of the hexagonal close packed structures.     

Test of advanced hyperfine structure theory by precision radio-frequency and laser spectroscopy in molybdenum

The hyperfine structure splittings of 32 even parity states and of 26 odd partity states of molybdenum have been measured by atomic beam magnetic resonance and by laser induced fluorescence. The analysis of the hyperfine structure data of the even parity configurations (4d+5s)⁶ yields experimental evidence for second order hyperfine interactions. In addition, theg _J factors of 19 fine structure levels have been determined in order to test the quality of intermediate coupling wave functions for the (4d+5s)⁶ configurations.     

Theoretical and experimental analysis of the fine structure and hyperfine structure in the configurations 5p6s and 5p6p of the antimony II spectrum

From 17 transitions in the singly ionized Sb II spectrum the hyperfine structure (A andB splitting constants) of the complete excited configurations 5p6s and 5p6p were determined by means of optical interference spectroscopy. In addition, a theoretical analysis both of the fine structure and also of the hyperfine structure was carried out (in the case of 5p6p of the general typenpn′p for the first time in literature). For the 3 levels 5p6p ³ P ₁, 5p7p ³ D ₂ and 5p6p ¹ P ₁ a different classification was found and consistent values for the fine structure parameters, mixing coefficients and single electron hyperfine structure splitting parametersa _nl ^ik andb _nl ^ik were obtained. The three new determinations in Sb II of the quadrupole moment (in barn) of¹²¹Sb (Q(5p6s)=?0.55(5);Q(5p6p)=?0.57(5) from the 5p-electron andQ(5p6p)=?0.7(2) from the 6p-electron) are well agreeing with each other but differ to former values from SbI. The core polarization and isotope shift of the lines, however, are compatible with our former results in SbI.     

Hyperfine structure and core polarization in Nd I 4f 4f 4 5d6s

The high resolution laser-atomic-beam technique was used to investigate the hyperfine structure in Nd I 4f ⁴ 5d6s ⁷ L, ⁷ K, ⁷ I, ⁷ H, ⁷ G, ⁵ L, ⁵ K, and ⁵ I for both of the stable odd isotopes. The metastable states were populated by an arc discharge burning in the atomic beam, and 31 transitions to higher odd levels have been studied. Knowledge of the hyperfine constants of 34 levels of 4f ⁴ 5d6s allowed a comprehensive parametric analysis to be performed, using the effective tensor operator formalism. Compared to earlier analyses, a significant reduction of errors has been achieved for all the parameters. The contact parameter a _4f ¹⁰ has been fitted freely, thus providing an experimental value for the core-polarization effects. They are about six times larger than the relativistic effects.     

Hyperfine structure in the configuration 4f 136s7s of Tm I

Doppler-free saturation absorption spectroscopy was applied on an atomic thulium vapour in a see-through hollow cathode for the determination of precise values for the magnetic dipole hyperfine structure constantsA of 6 levels of the configuration 4f ¹³ 6s7s. A parametric analysis of the hyperfine structure has been performed, using wave-functions from a fine structure calculation, which leads to one-electron hyperfine structure parametersa _4f ⁰¹ =?500(6) MHz,a _6s ¹⁰ =?5058(47) MHz, anda _7s ¹⁰ =?1012 MHz.     

Calculation of electron densities for EuI 4f 7(8 S)6s7s

Using the non-relativistic Hartree-Fock computer code of Froese Fischer, calculations have been performed for all terms of the configuration 4f ⁷(⁸ S)6s7s of EuI. The results are compared with recent isotope shift and hyperfine structure measurements. The calculated electron charge densities reproduce, up to a scaling factor, the experimental field shifts.     

ESR spectra of AsF2−6 and SbF2−6

ESR spectra observed in γ-irradiated CsAsF₆ and CsSbF₆ matrices have been assigned to the free radicals AsF^2?₆ and SbF^2?₆ respectively. The large, isotropic central-atom hyperfine interactions and isotropic g-values of these species suggest that they possess ²A_tg ground-states in O_h symmetry. The contribution to the semi-occupied orbital of the central-atom valence s atomic orbital is ≈ 0.6, greater than in the halogen hexafluorides (≈0.4) and the chalcogen hexafluoride anions (≈ 0.5). Variation of the central-atom hyperfine interaction with temperature is interpreted in terms of a second-order Jahn-Teller effect involving a low-lying ²T_1u excited state.     

Yb3CoSn6 and Yb4Mn2Sn5: New polar intermetallics with 3D open-framework structures

Two new ternary ytterbium transition metal stannides, namely, Yb₃CoSn₆ and Yb₄Mn₂Sn₅, have been obtained by solid-state reactions of the corresponding pure elements in welded tantalum tubes at high temperature. Their crystal structures have been established by single-crystal X-ray diffraction studies. Yb₃CoSn₆ crystallizes in the orthorhombic space group Cmcm (no. 63) with cell parameters of a=4.662(2), b=15.964(6), c=13.140(5) Å, V=978.0(6) Å³, and Z=4. Its structure features a three-dimensional (3D) open-framework composed of unusual [CoSn₃] layers interconnected by zigzag Sn chains, forming large tunnels along the c-axis which are occupied by the ytterbium cations. Yb₄Mn₂Sn₅ is monoclinic space group C2/m (no. 12) with cell parameters of a=16.937(2), b=4.5949(3), c=7.6489(7) Å, β=106.176(4)°, V=571.70(8) Å³, and Z=2. It belongs to the Mg₅Si₆ structure type and its anionic substructure is composed of parallel [Mn₂Sn₂] ladders interconnected by unusual zigzag [Sn₃] chains, forming large tunnels along the c-axis, which are filled by the ytterbium cations. Band structure calculations based on density function theory methods were also made for both compounds.     

Hyperfine structure in the configurations4f 4 6s 2 and4f 4 5d 6s of Nd I

The high resolution laser-atomic-beam technique was used to investigate the hyperfine structure in Nd I 4f ⁴6s ^{2 5} I,⁵ F,⁵ S and 4f ⁴5d6s ⁷ L,⁷ K,⁷ I,⁷ H. The metastable states were populated by an arc discharge burning in the atomic beam. The measured hyperfine constantsA andB of the levels of 4f ⁴6s ² and 4f ⁴5d6s allow a parametric analysis to be performed using the effective tensor operator formalism. The experimental radial integrals of the 4f and 5d electrons fit with those of the other lanthanides. The 4f radial integrals are in agreement with values of optimized Hartree-Fock-Slater calculations. The spectroscopic quadrupole moments of¹⁴³Nd and¹⁴⁵Nd are deduced from the 4f parameters:Q _I =?0.610(21) b and ?0.314(12) b, respectively. TheQ _I resulting from the 5d parameter are in satisfactory agreement with these values. The hyperfine anomaly due to thes electron in 4f ⁴5d 6s amounts to about 1%.     

Hyperfine structure measurements of the metastable (3d 6 4s 2)3 H 4, 5, 6 states of57Fe: Configuration interaction in the hyperfine structure of the iron atom

We report the hyperfine structure (hfs) measurement of the metastable (3d ⁶ 4s ²)a ³ H _{4, 5, 6} states of⁵⁷Fe. The kHz-precision of these experimental results together with the hyperfine structure values of (3d ⁶ 4s ²)a ⁵ D _{1, 2, 3, 4}, (3d ⁷ 4s)a ⁵ F _{2, 3, 4, 5}, and (3d ⁷ 4s)a ³ F _{2, 3, 4}, which were measured earlier, allowed to determine a very detailed set of effective radial parameters describing the hfs of these states, using a new parametrization method. This method treats one- and two-body contributions to the hfs separately. In this way configuration interaction effects in the hfs of the⁵⁷Fe atom can be studied in detail and compared with configuration interaction effects in the fine structure of the same atom.     

Optical detection of the ESR spectrum of hexafluorobenzene anion-radicals in squalane at room temperature

The technique of optical detection of ESR spectra from recombining radical pairs has been employed to observe the hyperfine structure of C₆F₆^? ion-radicals formed in squalane under ionizing irradiation. Anthracene introduced into the solution enhances the ESR intensity. The spectra are well described by second-order perturbation theory with a hyperfine interaction constant 133.6 G and g-value 2.0014.     

Experimental and theoretical study of the hyperfine structure in the (5d+6s)96p configurations of Pt I

The hyperfine structure of the odd configurations 5d ⁹6p and 5d ⁸6s6p was studied with laser optogalvanic spectroscopy and high resolution interferometry in a platinum hollow cathode. A parametric hyperfine structure analysis for the configurations (5d+6s)⁹6p with 10 excited odd-parity levels was performed for¹⁹⁵Pt. We obtained one-electron hfs parameters,a _5d ⁰¹ =1160(320) MHz,a _6s ¹⁰ =35600(5300) MHz anda _6p ⁰¹ =1300(780) MHz for the configuration 5d ⁸6s6p. The corresponding $\left\langle {r^{ - 3} } \right\rangle _{nl}^{k_s k_l } $ values are compared with those known for other 5d-elements.     

On the hyperfine structure in the configurations 4f n 6s 2, 4f n 5d6s, 4f n 6s6p,and 4f n−15d6s 2 of the lanthanides

A survey of hyperfine analyses in the low-lying configurations 4f ⁿ 6s ², 4f ⁿ 5d6s, 4f ⁿ 6s6p, and 4f ^n?1 5d6s ² of the lanthanides is given. Experimental hf radial integrals 〈r ^?3〉 _nl ^kj are indicated for the configurations under investigation. From a comparison of experimental and theoretical hf radial integrals configuration-interaction contributions Δ _nl ^kj to the hfs have been evaluated for the configurations for which corresponding integrals were available. With nuclear electric quadrupole moments from muonic x-ray investigations and radial integrals 〈r ^?3〉 _nl ⁰¹ and 〈r ^?3〉 _nl ⁰² from experimental hfs quadrupole shielding correctionsR _nl ⁰¹ have been obtained. The variation of hyperfine radial integrals, configuration-interaction contributions and quadrupole shielding corrections over the 4f shell in the configurations under study is discussed. Trends of these quantities in different configurations are compared.     

Laser-Rf double-resonance measurements of the metastable 3d 34s 5P1,2,3, 3d 24s 2 1 G 4 states of 47Ti

The hyperfine structure (hfs) of 4 metastable states of ⁴⁷Ti has been measured very precisely by a laser-rf double resonance method. The corresponding hyperfine structure constants A _exp and B _exp have supplied a set of experimental data necessary for hyperfine structure analysis and determination of Sternheimer free nuclear quadrupole moment Q.