The hyperfine structure in the configuration 4f 135d6s6p in ytterbium

Using Doppler-reduced laser induced fluorescence spectroscopy in an atomic beam, the hyperfine structure of 22 levels of the configuration 4f ¹³5d6s6p in neutral ytterbium has been investigated for the two odd isotopes ¹⁷¹ Yb and ¹⁷¹ Yb. The experimental results have been used in a study of the hyperfine structure in regard to a determination of the one-electron parameters for the magnetic dipole and the electric quadrupole hyperfine coupling of the isotope ¹⁷³ Yb in part II of this work.     

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%.     

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.     

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.     

Effect of presence of 18-crown-6 on the response of 1-pyrrolidine dicarbodithioate-based lead selective electrode

The lipophilic ammonium salt of 1-pyrrolidine dicarbodithioic acid (PCDT)[I] was introduced as a selective ionophore for a sensitive Pb-ion selective electrode. Also, the effect of immobilization of 18-crown-6 (CW), into the above membrane, on the electrode performance was discussed. The slope of the PCDT-based [I] electrode was (26–30 mV decade⁻¹), while it was (29-30 mV decade⁻¹) for (PCDT+CW)-based [II] electrode according to the doping time. The linear concentration ranges were (1×10⁻⁶–1×10⁻¹ M) and (5×10⁻⁵–1×10⁻¹ M) for electrode types [I] and [II] after one-day doping. The working pH ranges were (5.0–10.0) and (7.0–10.0) for electrode types [I] and [II], respectively. Most of the common cations were tested for the evaluation of the electrode selectivity with correlation to the ionic radii of the tested cations. Among them only Na⁺, Ag⁺ and Fe³⁺ were the real interference. Application of using the electrode for the determination of lead in lubrication oil samples was performed with RSD (0.86–1.03%). The obtained results were compared to those of an atomic absorption spectrophotometric method.     

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.     

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.     

Laser and radiofrequency spectroscopy of the 5d 4 6s 6 D multiplet in Ta I

The hyperfine structure (hfs) of¹⁸¹Ta has been investigated using laser radio-frequency double resonance and high resolution laser spectroscopy on collimated atomic beams. The magnetic dipole and electric quadrupole hyperfine structure coupling constants of the 5d ^{4 6} s 6D _{3/2, 5/2, 7/2, 9/2} metastable states have been determined using radio-frequency spectroscopy. In the 5d ⁴ 6s ⁶ D _1/2 metastable state and the excited 5d ³ 6s 6p ⁴ D _3/2,⁶ D _{5/2, 9/2} as well as the unidentified 28 182.6 cm^–1 and 30 021.2 cm^–1 states, hfs constants have been obtained from high resolution laser spectroscopy. A radio-frequency converter has been developed in order to reach the frequency region 2.7–10 GHz.     

Kinetic investigation of electronic energy transfer processes following the pulsed dye-laser generation of excited atomic barium, Ba[6s6p(P1)], in the presence of atomic strontium

The collisional behaviour of Ba[6s5d(³D_J)], 1.151 eV above the 6s²(¹S₀) electronic ground state, in the presence of atomic strontium, has been investigated in the ‘long-time domain' (ca. 100 μs–1 ms) following the pulsed dye-laser excitation of barium vapour at elevated temperature at λ = 553.5 nm (Ba[6s6p(¹P₁)] ← Ba[6s²(¹S₀)]. Ba(³D_J) is subsequently produced from the short-lived ¹P₁ state (τ_e = 8.37 ± 0.38 ns) by a number of radiative and collisional processes. It may then be monitored in the ‘long-time domain' by atomic spectroscopic marker methods involving either collisional activation of Ba(³D_J) by Ba(¹S₀) and He buffer gas to yield Ba[6s6p(³P_J)] with subsequent emission from the ³P₁ state (τ_e = 1.2 ± 0.1 μs): Ba[6s6p(³P₁)] → Ba[6s²(¹S₀)] + hv (λ = 791.1 nm). Alternatively, emission from Ba(¹P₁) may be monitored at long times following the generation of this short-lived state by energy pooling following self-annihilation of Ba(³D_J) + Ba(³D_J) from Ba[6s6p(¹P₁)] → Ba[6s²(¹S₀)] + hv (λ = 553.5 nm). The generation of Ba(³D_J) in the presence of atomic strontium yields emission in the long-time domain from Sr[5s5p(³P₁)] (τ_e = 19.6 μs): Sr[5s5p(³P₁)] → Sr[5s²(¹S₀)]  + hv (λ = 689.3 nm). Whilst the decay profiles at short times are complex in form, at long times all these atomic profiles show first-order kinetic removal with the decay coefficients for λ = 791.1 nm, 689.3 nm and 553.5 nm emissions in the ratio 1 : 2 : 2, consistent with overall third-order activation of the form: Ba(³D_J) + Ba(³D_J) + Sr(¹S₀) → Sr(³P_J) + 2Ba(¹S₀). The mechanism is modelled in detail, including measurement of integrated emission intensities, yielding kinetic data for fundamental collisional processes. The overall rate constant for the third-order collisional activation of Sr[5s5p(³P_J])from 2Ba[6s5d(³D_J)] + Sr[5s²(¹S₀)] takes the upper limit of 5.8 × 10⁻²⁷ cm⁶ atom⁻² s⁻¹ (T = 900 K). The rate constant for the two body collisional quenching of Ba[6s5d(³D_J)] by ground state atomic strontium, Sr[5s²(¹S₀)], is found to be (2.0 ± 0.1) × 10⁻¹² cm³ atom⁻¹ s⁻¹ (T = 900 K).     

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.     

Studies on Co(II) and Co(III) complexes of di-2-pyridyl ketone N(4)-cyclohexyl and N(4)-phenyl thiosemicarbazones

Six new Co(II) and Co(III) complexes (1–6) of di-2-pyridyl ketone N(4)-cyclohexyl thiosemicarbazone (HL¹) and di-2-pyridyl ketoneN(4)-phenyl thiosemicarbazone (HL²) have been synthesized and spectrochemically characterized. HL¹ is newly synthesized and has been structurally characterized by single crystal X-ray diffraction studies, while HL² has been previously reported. HL¹ crystallizes into a monoclinic lattice with the space group P2₁. The complexes are characterized by magnetic, EPR, NMR and other spectroscopic studies. The EPR spectra of the paramagnetic complexes reveal axial features with eight hyperfine lines clearly resolved in the perpendicular region.     

Application of a new resin functionalised with 6-mercaptopurine for mercury and silver determination in environmental samples by atomic absorption spectrometry

Polystyrene–divinylbenzene (8%) has been functionalised by coupling it through an ---N=N--- group with 6-mercaptopurine. The resulting chelating resin has been characterised by using elemental analysis, thermogravimetric analysis and infrared spectra. The resin is highly selective for Hg(II) and Ag(I) and has been used for preconcentrating Hg(II) and Ag(I) prior to their determination by atomic absorption spectrometry. The maximum sorption capacity for Hg(II) and Ag(I) was found to be 1.74 and 0.52 mmol g⁻¹, respectively, over the pH range 5.5–6.0. The calibration range for Hg(II) was linear up to 10 ng ml⁻¹ with a 3σ detection limit of 0.02 ng ml⁻¹; the calibration range for Ag(I) was linear up to 5 μg ml⁻¹ with a detection limit of 29 ng ml⁻¹. The recoveries of the metals were found to be 99.7±3.8 and 101.3±4.1% at the 95% confidence level for both Hg(II) and Ag(I). In column operation, it has been observed that Hg(II) and Ag(I) in trace quantities can be selectively separated from geological, medicinal and environmental samples.     

Stark and Zeeman spectroscopies of 4f 66s6p 7G1-6 levels in Sm I under external electric and magnetic fields

Systematic study of hyperfine structures, Zeeman and Stark effects in Sm I is performed for the lowest ⁷G_1-6 levels belonging to the configuration 4f ⁶6s6p by atomic-beam laser spectroscopy with fluorescence detection. The hyperfine coupling constants of ⁷G_2-6 levels are determined. From the Zeeman splittings for the 4f ⁶6s ^{2 7}F_2-6 ? 4f ⁶6s6p ⁷G_2-6 transitions, g-values are determined for the ⁷G_2.6 levels and the precision is improved by several orders of magnitude. From the Stark splittings for the ⁷F_0-3 ? ⁷G_1-3 transitions, tensor polarizabilities α ₂(J) are determined for the upper ⁷G_1-3 levels. Particularly for the ⁷G₁ level (15 650.55 cm^?1) which has close-lying opposite-parity level, the isotope dependence of α ₂(J) is clearly observed for the first time.     

J-dependence of the isotope shift in Eu I 4f 75d6s(a 6 D)

The J-dependence of the isotope shift (IS) in the term a⁶D of the Eu I configuration 4f⁷5d6s was determined to be: z_5d(⁶D)=+34.5(1.5) MHz. This proves that in the phenomenological interpretation of the IS distinct parameters z_nl(^mL) for the J-dependence in one term are necessary.     

Mössbauer study of the Sn resonance in rare-gas matrix-isolated Sn(IV)-and Sn(II)halide molecules

Mössbauer absorption spectra of rare-gas matrix-isolated SnX₄ and SnX₂ molecules (X = F, Cl, Br, I) have been measured at matrix temperatures of a bout 5 K. The hyperfine interaction (hfi) parameters of ¹¹⁹Sn in argon matrix-isolated SnX₄ (X = Cl, Br, 1) molecules are identical with those of the corresponding crystalline compounds. This fact reveals that the inter-molecular interactions are negligible in the crystalline compounds as far as concerning the electronic structure of Sn⁴⁺. The ¹¹⁹Sn hfi parameters of rare-gas matrix-isolated SnX₂ molecules differ from those measured in the crystallin compounds. This arise from the totally different coordination of tin in the two situations. The analysis of the hfi parameters using a simple bonding model yields information about the ionicity of the Sn-halogen bonds and the bonding angle in these molecules. The observed isomer shifts and quadrupole interactions can only be explained in this model with a bonding angle θ = 95° ± 2° for all SnX₂ molecules and a slight increase of θ from Sn1₂ to SnF₂.     

Crystallographic evidence for different modes of interaction of BF3/BF4 species with water molecules and 18-crown-6

We report the crystal and molecular structures of the complex of 18-C-6 with H₃O⁺BF₄⁻ (I) and the complex of 18-C-6 with BF₃OH₂·H₂O (II). The different modes of appearance of the “BF₃” species as BF₃, BF₃OH₂, BF₃OH₂·H₂O and BF₄⁻, as well as their structurally significant intermolecular and intramolecular interactions, are discussed. In complex I the oxonium ion is bound at the centre of the 18-C-6 macrocycle. The oxonium oxygen is located practically equidistant (2.68–2.73 Å) from the six macrocyclic ethereal oxygens. The BF₄⁻ counter-ion is positioned 7.3 Å away from the oxonium ion in the same general plane of the crown ether. This anion is not involved in any direct intermolecular contacts, a fact that may explain why it is spherically disordered. In complex II there is no guest molecule (or ion) present in the “cavity” of the macrocycle, but there are two hydrogen-bonded systems of BF₃OH₂·H₂O that are interacting with the crown ether on either side of the general macrocyclic plane. Complex II features three types of hydrogen bonds—the O(water)-HO(crown) bonds (2.83 and 2.85 Å), the O(water)H-O(BF₃) bond (2.49 Å) and the O(BF₃)-HO(crown) bond (2.65 Å). The strong intermolecular O(crown)O(water)O(BF₃) and O(crown)O(BF₃) interactions stabilize the normally unstable BF₃OH₂·H₂O species.     

Wavelength and isotopic shift measurements of the3S(3s 4s) −3P(3s 3p) MgI transitions

The wavelengths of the³S(3s 4s) ?³P(3s 3p) MgI transitions have been measured for the²⁴Mg isotope with a precision of ±2 × 10^?7; moreover the isotope shifts of the above transitions have been measured for the three natural Mg isotopes as well as the hyperfine constants of the³S(3s 4s) level of²⁵Mg. The measurements have been performed in a metastable atomic beam.     

Studies on long lasting optical properties of Eu2+ and Dy3+ doped di-barium magnesium silicate phosphors

Di-bariummagnesium silicate phosphors doped with europiumand dysprosium were prepared under a weak reducing atmosphere. X-ray diffraction pattern of the sample was also done that confirmed the proper preparation of the phosphor. Scanning electron microscope (SEM) images confirmed that the sample has regular surface and uniform grain size distribution. Comparative studies of phosphorescence decay of Ba₂MgSi₂O₇:Eu²⁺, Dy³⁺ phosphors with different concentration of Dy³⁺ were done. The phosphor with 0.5/1.5 mol% of Eu/Dy, exhibited optimum green color afterglow properties. This emission is expected to arise due to transition of Eu²⁺ ions from any of the sublevels of 4f⁶5d¹ configuration to ⁸S_7/2 level of the 4f⁷ configuration. For a suitable trap depth, the trap concentration is expected to be proportional to the concentration of Dy³⁺. These traps are responsible for holding the charge career for a reasonable time, subsequently for increasing the time of afterglow. Hence, optimum Dy³⁺ concentration produces the longer afterglow duration with higher intensity of luminescence signals. Trap depth were also calculated using thermoluminescence glow curve which was indicative of formation of traps suitable for long afterglow.     

Atomic charge distribution in 4-isopropylphenol molecule derived from atomic polar tensors

On the basis of the calculated atomic polar tensors the generalized atomic polar tensor charges have been calculated for 4-isopropylphenol (4-IP) and related compounds: benzene, quinone, phenol and p-nitroaniline (p-NA). The second order Möller–Plesset perturbation method and Huzinaga–Dunning's double valence ζ basis set supplemented by d polarisation function on heavy atoms and p on hydrogen atoms (D95V^**) have been used. Analysis of the atomic charges has been done. It is found that the phenyl rings of the 4-IP and p-NA molecules have an intermediate structure between the aromatic ring and the quinoid one.     

Eu2+掺杂KCaCl3晶体的生长及发光性能

通过坩埚下降法生长出不同物质的量分数Eu²⁺掺杂的KCa_1-xEu_xCl₃(x=0.005、0.01、0.02、0.03、0.05)单晶,并对晶体进行了X射线粉末衍射、热重、透过率、光致发光光谱、衰减时间、X射线激发发射光谱等测定。通过相图及结构分析,判断出该晶体为一致熔融化合物,并得出其为正交结构,晶胞参数为a=0.75604 nm,b=1.04823 nm,c=0.72657 nm,空间群为Pnma(62)。在紫外光的激发下,晶体在434 nm左右有一个宽的发射峰,对应于Eu²⁺的4f⁶5d¹→4f⁷跃迁;光致衰减时间1.473μs,晶体在X射线激发下的发光强度随Eu²⁺离子浓度增加而增强。