Term isotope shift of high lying odd and even energy levels of Nd II

The isotope shifts of the odd and even parity energy levels of singly-ionised neodymium (Nd II) have been evaluated using the measurements carried out in more than 300 spectral lines of Nd II in the region 3290–5820 Å. Term shift, ΔT (¹⁴⁴Nd-¹⁵⁰Nd), is being reported for 23 low even and 15 high lying even parity levels of Nd II. ΔT for a level of 4f ³6s6p configuration and 8 even levels between 36892 and 43212 cm^-1 are being reported for the first time. ΔT values of 151 high lying odd parity levels are being reported and compared with some of the available earlier reported values. ΔT values of 47 odd parity levels are being reported for the first time, most of which are based on our isotope shift studies in UV region. The electronic configuration assignments to energy levels of Nd II by earlier workers are discussed on the basis of present ΔT values. Electronic configurations to some of the unclassified high lying odd levels have been suggested; the levels with ΔT (144–150) between 300mK and 380mK are assigned to 4f ³5d6s configuration whereas a level with ΔT value of 60mK to 4f46p configuration.     

Isotope shift studies in the second spectrum of neodymium in UV region

Isotope shift (IS) Δσ (142–150) have been measured in 92 spectral lines of Nd⁺ in the region 3290–3955 Å, employing recording Fabry-Perot spectrometer and highly enriched isotopic samples excited in a liquid-nitrogen cooled hollow cathode. Earlier IS measurement in UV region of Nd II spectrum is available for only a few lines, New classification has been made for several of the spectral lines studied presently. We have also revised the earlier suggested classification for some of the Nd II lines on the basis of observed isotope shifts. The transitions presently studied mostly involve high lying odd parity energy levels above 30,000 cm^?1 having neither electronic configuration assignment nor term isotope shifts (ΔT) evaluated. The present study would thus enable to evaluate ΔT values of some of these high lying odd levels, which should be helpful in suggesting possible electronic configurations.     

Isotope shift studies in the UV spectrum of singly ionised gadolinium

Isotope shift Δσ(¹⁵⁶Gd-¹⁶⁰Gd) are reported for 33 spectral lines of singly ionised gadolinium (Gd II) in the 3315–3930 Å region, making use of a photoelectric recording Fabry-Perot spectrometer and highly enriched isotopic samples of ¹⁵⁶Gd and ¹⁶⁰Gd Isotope shift values for these lines have not been reported earlier. Using this data, term isotope shift ΔT(¹⁵⁶Gd-¹⁶⁰Gd) have been evaluated for the even and odd parity energy levels involved in these transitions. We report here ΔT values of only 10 odd parity energy levels lying above 35 000 cm⁻¹, which have been evaluated for the first time. Configuration assignments of six of these levels to 4f⁸6p have been confirmed and probable configurations suggested for four unassigned levels.     

Isotope shifts in spectral lines of Yb+ in 322-615nm region and term shifts of odd and even parity energy levels of Yb II

Isotope shift Δσ(¹⁷²Yb - ¹⁷⁶Yb) has been measured in 79 classified lines of Yb II in the region 3225-6155 Å. Earlier studies provide isotope shift data in just six lines of Yb II. Term isotope shift ΔT (¹⁷²Yb-¹⁷⁶Yb) have been evaluated for 38 even and 30 odd parity levels of Yb II, using the present isotope shift data. The ΔT values have been discussed and correlated with the purity of the configuration assigned to an energy level, which enabled to check the reported eigenvector percentages of different configurations for some of the levels of Yb II. ΔT values of different levels resulting from J_IL_II couplings are also discussed.     

Isotope shift studies in the spectra of Gadolinium in UV region and term shifts of high even levels of Gd I

Isotope shift Δσ(¹⁵⁶Gd?¹⁶⁰Gd) is reported in 70 spectral lines of neutral gadolinium atom (Gd I) in the 3290- 3920 Å region providing isotope shift data in UV lines of Gd I spectrum for the first time. The measurements were carried out on a photoelectric recording Fabry-Perot Spectrometer using highly enriched isotopic samples of gadolinium. Term isotope shifts ΔT(¹⁵⁶Gd?¹⁶⁰Gd) have been evaluated for 48 high lying even parity energy levels of Gd I using this data; new ΔT values have been obtained for 24 levels. Electronic configurations 4f⁷5d6s6p, 4ff⁷5df²6p and 4f⁸5d6s assigned earlier to these even levels have been either confirmed or configuration mixing pointed out in some of these levels. Probable assignment of 4f⁸5d6s configuration to 8 even levels between 32 930 and 35 500 cm^-1 have been confirmed.     

Isotope shift studies and electronic configuration assignments to the energy levels of neutral erbium

Isotope shifts ΔT (170-166) have been evaluated for 54 even and 94 odd energy levels covering almost all the known configurations of the neutral erbium. These ΔT values have been derived from the isotope shift measurements carried out in 159 lines in the region 3900–4605 A using a Fabry-Perot spectrometer and liquid-air-cooled hollow cathode source with highly enriched ¹⁷⁰Er and ¹⁶⁶Er isotopic samples. Electronic configurations assigned to energy levels of Er I by earlier workers have been mostly confirmed and in few cases revisions have been suggested on the basis of observed ΔT values. Probable configurations have been also suggested for unassigned levels of Er I, and a large number of even levels could be assigned to 4f¹¹ 5d 6s 6p configuration.     

Isotope shifts in energy levels of the neutral neodymium atom

Isotope shift ΔT(142–144) have been evaluated for 281 odd and 110 even levels of the neutral neodymium atom from the isotope shift measurements made in the classified lines of Nd I spectra covering the region 3930–6510 Å. These investigations were carried out on a recording Fabry—Perot spectrometer using enriched isotopes excited in liquid-air cooled hollow cathodes. Electronic configurations of the energy levels have been discussed and probable configurations assigned to many odd and even levels. Most of the high even levels could be assigned to 4f³5d²6p configuration.     

Isotope shifts in the energy levels of the singly ionized neodymium atom

Isotope shifts ΔT (142–144) have been evaluated for odd and even energy levels of the singly ionised neodymium atom from the measurements carried out in 168 spectral lines in the 3930–5820 Å region, employing a recording Fabry-Perot spectrometer and highly enriched isotopes excited in liquid-air cooled hollow cathodes. The electronic configurations 4f³5d6s, 4f³5d6p and 4f⁴6p could be assigned to some of the energy levels on the basis of the present study.     

Isotope shifts and electronic configurations of some of the energy levels of the neutral gadolinium atom

Isotope shift ΔT (156–160) have been evaluated for 52 odd and 90 even energy levels of the neutral gadolinium atom from the measurements carried out on 166 lines of the first spectrum in the region 4535–4975 Å on a photoelectric recording Fabry-Perot Spectrometer and enriched samples of ¹⁵⁶Gd and ¹⁶⁰Gd. Earlier studies provide data for just two lines in this region. Assignment of electronic configurations to some of the energy levels have been either confirmed or revised; some unassigned levels have been assigned probable configurations. The present study provides, for the first time, isotope shift of the two levels of 4f⁷6s²7 s configuration of Gd I.     

Reevaluation of term isotope shifts of low even levels of 4f86s2 configuration and high odd-parity levels of neutral gadolinium atoms

Isotope shift ΔT(¹⁵⁶Gd–¹⁶⁰Gd) of the even-parity energy levels of 4f⁸6s² and 4f⁷6s²6p configurations of neutral gadolinium atoms (Gd I) have been reevaluated using the level isotope shift (ΔT) of two odd-parity levels reported recently. Earlier the isotope shifts of these even-parity energy levels were evaluated using empirical relation. Our extensive isotope shift data has been used for the reevaluation of ΔT values of these low even-parity energy levels which have been utilised for revision of the ΔT values of high-lying odd-parity energy levels of Gd I.     

Determination of crossed-second-order field shift in8 F and6 F terms of 4f 6(7 F)6s configuration of sm+

We report here the experimental evaluation of crossed-second-order (CSO) effects in the field shift of⁸ F and⁶ F terms of 4f ⁶(⁷ F)6s configuration of singly ionised samarium. Our experimental value of CSO field shift difference between⁸ F and⁶ F terms for¹⁴⁸Sm and¹⁵⁴Sm is ?11.8(3.2) mK, which is in good agreement with the theoretical value of ?13.8 mK evaluated using known parameters.     

Laser spectroscopic investigation of isotope shifts in Nd II lines

The isotope shift of 11 optical transitions in Nd II in the spectral range 420–450 nm have been recorded (in all cases but one for all pairs of even Nd isotopes). For all observed transitions the values of the field shifts, the specific mass shifts and Δ∣ψ(0)∣² have been evaluated. Using our new data, combined with data reported in earlier papers, term isotope shifts for all pairs of even Nd isotopes have been determined for 27 energy levels and for the configurations: 4f⁴6s, 4f⁴5d, 4f³5d6s and 4f⁴6p as well. It is shown that configuration assignment of a level on the basis of term shift values only is in some cases not satisfactory (as e.g. of the level at 22,696 cm⁻¹) and obviously additional information is required.     

Isotope shift in chromium

Thirty-three spectral lines of chromium atom in the blue-violet region (425–465 nm) have been investigated with the method of laser-induced resonance fluorescence on an atomic beam. For all the lines, the isotope shifts for every pair of chromium isotopes have been determined. The lines can be divided into six groups, according to the configuration of the upper and lower levels. Electronic factors of the field shift and the specific mass shift (F_ik and M_ik^SMS, respectively) have been evaluated and the values for each pure configuration involved have been determined. Comparison of the values F_ik and M_ik^SMS to the ab initio calculations results has been performed. The presence of crossed second order (CSO) effects has been observed.     

Photofunctional supramolecular solution systems of chiral Schiff base nickel(II), copper(II), and zinc(II) complexes and photochromic azobenzenes

Preparations, crystal structures, electronic and CD spectra are reported for new chiral Schiff base complexes, bis(N-R-1-naphthylethyl-3,5-dichlorosalicydenaminato)nickel(II), copper(II), and zinc(II). Nickel(II) and copper(II) complexes adopt a square planar trans-[MN₂O₂] coordination geometry with Δ(R,R) configuration. While zinc(II) complex adopts a compressed tetrahedral trans-[MN₂O₂] one with Δ(R,R) configuration and exhibits an emission band around 21 000 cm⁻¹ (λ_ex = 27 000 cm⁻¹). Absorption and CD spectra were recorded in N,N′-dimethylformamide, acetone, methanol, chloroform, and toluene solutions to discuss relationships between spectral shifts of d–d and π–π^∗ bands by structural changes of the complexes and physical properties of the solvents. Moreover, we have attempted to investigate conformational changes of the complexes induced by photoisomerization of azobenzene, 4-hydroxyazobenzene, or 4-aminoazobenzene, in various solutions under different conditions. Weak intermolecular interactions between complexes and azobenzenes are important for the phenomenon by conformational changes of bulky π-conjugated moieties of the ligands.     

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.     

Electronic configurations and isotope shifts of the energy levels of the neutral dysprosium atom

Electronic configurations of the energy levels of the neutral dysprosium atom have been suggested on the basis of isotope shift studies carried out in the first spectrum of dysprosium using highly enriched isotopes excited in liquid-air-cooled hollow cathode lamps and a photoelectric recording Fabry-Perot spectrometer. Isotope shift Δ T(164-160) have been evaluated for 85 even and 82 odd energy levels. The configurations 4f⁹d6s6p, 4f⁹6p6s² and 4f¹⁰6s6d along with two new configurations 4f⁹5d²6p and 4f¹⁰6p² have been assigned to even levels whereas the configurations 4f⁹5d²6s, 4f¹⁰6s6p and 4f¹⁰5d6p have been assigned to some odd energy levels of the neutral dysprosium atom.     

Stark broadening and shift of multiply ionized carbon spectral lines

Stark widths and shifts of sixCII, threeCIII and twoCIV spectral lines have been measured in a linear pinch discharge plasma and compared with available experimental and theoretical data. Electron density, (0.86?1.64)×10²³ m^?3, was determined by single wavelength laser interferometry using the visible 632.8 nm transition of He-Ne laser. The electron temperature of 38000 K was derived from the Boltzmann slope of severalCII spectral lines, and ratios of severalCII toCIII spectral lines. The stark widths (w) dependence on:(i) the upper-level ionization potential (I) of corresponding lines;(ii) net charge (z) of the emitter core seen by the optical electron undergoing transition, and(iii) electron temperature (T) was found to be of the form:w=az ² T ^?1/2 I ^?b . However, it should be noticed that the essential role in the obtained trends belongs to the energy of the emitter core. The established overall trend is used to predict Stark widths of uninvestigated spectral lines originating from the given transition arrays.     

Isotope shifts in odd and even energy levels of the neutral and singly ionised gadolinium atom

Isotope shift studies in the gadolinium spectra have been extended in the region 4140–4535 Å. Isotope shift Δσ(156–160) have been measured in 315 lines of the neutral and singly ionised galolinium atom using a recording Fabry—Perot Spectrometer and gadolinium samples enriched in ¹⁵⁶Gd and ¹⁶⁰Gd isotopes. Some of the Gd I lines studied involve transitions from newly identified high odd levels of 4f⁸6s 6p, 4f⁷5d 6s 7s and 4f⁷5d³ configurations to low even levels of 4f⁸6s² and 4f⁷6s²6p configurations. Electronic configurations of the energy levels have been discussed on the basis of observed isotope shifts. In some cases assigned configurations have been revised and probable configurations have been suggested.     

Hyperfine structure studies of Tantalum

A narrow bandwidth ring dye laser pumped by an argon ion laser has been used to investigate the hyperfine structure of the even and odd parity levels of tantalum by optogalvanic spectroscopy in the wavelength range 5640 to 6050 Å. Seventeen transitions have been observed and eight of these have not been reported in the literature so far. These transitions involve 27 levels with 15 odd and 12 even parity configurations. The magnetic dipole hyperfine interaction constants A and the electric quadrupole interaction constants B for these levels have been computed and compared with the data available in literature. The results for the levels at 34799.71 cm^?1, 26960.46 cm^?1 and 19657.78 cm^?1 are reported for the first time.     

Inversion of tetrahedral configuration of bis-{4-aminomethylenepyrazole-5-thion(seleno)ato} nickel(II) complexes

Novel bis-chelate Ni(II) complexes with a series of 1,3-disubstituted 4-aminomethylenepyrazole-5-thion(seleno) derivatives have been prepared. An inversion of the tetrahedral configuration at the metal centre in these complexes proceeds in solution via the intramolecular diagonal twist rearrangement on the NMR time scale which was followed by coalescence studies on several pairs of diastereotopic protons. The activation barriers are: ΔG²(T_c) = 41–74 kJ mol^?1, _c = 218–373 K. The bulky substituents R₃ at the aldimine nitrogen give rise to significant increases in the energy barriers to enantiomerization of tetrahedral complexes owing to the steric hindrance involving an intermediate square planar form.