Quadrupole Line Research Articles

Study of the velocity-selection satellites present in the () electric quadrupole transitions in atomic rubidium

This article presents detailed experimental and theoretical studies of the satellite fluorescence lines observed when the , (, ) electric quadrupole transition (E2) is excited in a room temperature vapor of rubidium atoms. The initial state of this E2 transition is prepared by a narrow linewidth (9 MHz) laser locked to one of the dominant D2 hyperfine excitations for zero-velocity atoms. Effects due to the selection of different atomic velocity classes in this preparation step are responsible for the presence of several satellite lines that can be found in the fluorescence decay spectra of both 85Rb and 87Rb. Compared to the main lines, these satellites do not show a strong dependence on the relative linear polarization directions of the lasers used in the preparation and the electric quadrupole steps. The relative intensities of the satellites decrease as the intensity of the preparation laser increases. Results of a rate equation calculation that explicitly includes selection-of-velocity effects indicate that optical pumping plays a central role in determining the relative intensities and the polarization dependence of the satellite lines. When the preparation laser is locked to the low-F cyclic transition in 87Rb, six lines were found in addition to the lone electric quadrupole transition for zero velocity atoms. In this case, the calculated spectrum is necessary for the correct interpretation of the experimental results, clearly indicating that optical pumping and selection of velocities are responsible for these six additional electric quadrupole lines.

Lamb Dip of a Quadrupole Transition in H_{2}.

The saturated absorption spectrum of the hyperfineless S(0) quadrupole line in the (2-0) band of H_{2} is measured at λ=1189 nm, using the NICE-OHMS technique under cryogenic conditions (72K). It is the first time that a Lamb dip of a molecular quadrupole transition has been recorded. At low (150-200W) saturation powers a single narrow Lamb dip is observed, ruling out an underlying recoil doublet of 140kHz. Studies of Doppler-detuned resonances show that the redshifted recoil component can be made visible for low pressures and powers, and prove that the narrow Lamb dip must be interpreted as the blue recoil component. A transition frequency of 252 016 361 164 (8)kHz is extracted, which is off by -2.6 (1.6)MHz from molecular quantum electrodynamical calculations therewith providing a challenge to theory.

A stimulated Raman loss spectrometer for metrological studies of quadrupole lines of hydrogen isotopologues

We discuss layout and performance of a high-resolution Stimulated Raman Loss spectrometer that has been newly developed for accurate studies of spectral lineshapes and line centre frequencies of hydrogen isotopologues and in general of Raman active transitions. Thanks to the frequency comb calibration of the detuning between pump and Stokes lasers and to an active alignment of the two beams, the frequency accuracy is at a level of 50 kHz. Over the vertical axis the spectrometer benefits from shot-noise limited detection, signal enhancement via multipass cell, active flattening of the spectral baseline and measurement times of few seconds over spectral spans larger than 10 GHz. Under these conditions an efficient averaging of Raman spectra is possible over long measurement times with minimal distortion of spectral lineshapes. By changing the pump laser, transitions can be covered in a very broad frequency span, from 50 to 5000 cm−1, including both vibrational and rotational bands. The spectrometer has been developed for studies of fundamental and collisional physics of hydrogen isotopologues and has been recently applied to the metrology of the Q(1) 1–0 line of H2.

Observation of electric-quadrupole infrared transitions in water vapor

Molecular absorption of infrared radiation is generally due to ro-vibrational electric-dipole transitions. Electric-quadrupole transitions may still occur, but they are typically a million times weaker than electric-dipole transitions, rendering their observation extremely challenging. In polyatomic or polar diatomic molecules, ro-vibrational quadrupole transitions have never been observed. Here, we report the first direct detection of quadrupole transitions in water vapor. The detected quadrupole lines have intensity largely above the standard dipole intensity cut-off of spectroscopic databases and thus are important for accurate atmospheric and astronomical remote sensing.

Hydrogen Dimers in Giant-planet Infrared Spectra

Abstract Despite being one of the weakest dimers in nature, low-spectral-resolution Voyager/IRIS observations revealed the presence of (H2)2 dimers on Jupiter and Saturn in the 1980s. However, the collision-induced H2–H2 opacity databases widely used in planetary science have thus far only included free-to-free transitions and have neglected the contributions of dimers. Dimer spectra have both fine-scale structure near the S(0) and S(1) quadrupole lines (354 and 587 cm−1, respectively), and broad continuum absorption contributions up to ±50 cm−1 from the line centers. We develop a new ab initio model for the free-to-bound, bound-to-free, and bound-to-bound transitions of the hydrogen dimer for a range of temperatures (40–400 K) and para-hydrogen fractions (0.25–1.0). The model is validated against low-temperature laboratory experiments, and used to simulate the spectra of the giant planets. The new collision-induced opacity database permits high-resolution (0.5–1.0 cm−1) spectral modeling of dimer spectra near S(0) and S(1) in both Cassini Composite Infrared Spectrometer observations of Jupiter and Saturn, and in Spitzer Infrared Spectrometer (IRS) observations of Uranus and Neptune for the first time. Furthermore, the model reproduces the dimer signatures observed in Voyager/IRIS data near S(0) on Jupiter and Saturn, and generally lowers the amount of para-H2 (and the extent of disequilibrium) required to reproduce IRIS observations.

Benchmarking Atomic Data for Astrophysics: Be-like Ions between B ii and Ne vii

Large-scale self-consistent multiconfiguration Dirac--Hartree--Fock and relativistic configuration interaction calculations are reported for the $n \leq 6$ levels in Be-like ions from B II to Ne VII. Effects from electron correlation are taken into account by means of large expansions in terms of a basis of configuration state functions, and a complete and accurate data set of excitation energies, lifetimes, wavelengths, and electric dipole, magnetic dipole, electric quadrupole, and magnetic quadrupole line strengths, transition rates, and oscillator strengths for these levels is provided for each ion. Comparisons are made with available experimental and theoretical results. The uncertainty of excitation energies is assessed to be 0.01\% on average, which makes it possible to find and rule out misidentifications and aid new line identifications involving high-lying levels in astrophysical spectra. The complete data set is also useful for modeling and diagnosing astrophysical plasmas.

Rovibrational line-shape parameters for H2 in He and new H2-He potential energy surface

We report a new H2-He potential energy surface that, with respect to the previous one [Bakr et al.(2013)], covers much larger range of H2 stretching and exhibits more accurate asymptotic behavior for large separations between H2 and He. Close-coupling calculations performed on this improved potential energy surface allow us to provide line shape parameters for H2 between 5 and 2000 K for Raman isotropic Q lines and anisotropic Q lines (or electric quadrupole lines) and for vibrational bands from the ground up to v=5 and rotational quantum numbers up to j=5. The parameters provided include the usual pressure -broadening and -shifting coefficients as well as the real and imaginary part of Dicke contribution to the Hess profile. The latter parameters can be readily implemented in other line-shape profiles like the most recent one of Hartmann and Tran.

Calculations for energies, transition rates, and lifetimes in Al-like Kr XXIV

Using the second-order many-body perturbation theory (MBPT) method, a complete and accurate data set of excitation energies, lifetimes, wavelengths, and electric dipole (E1), magnetic dipole (M1), electric quadrupole (E2), and magnetic quadrupole (M2) line strengths, transition rates, and oscillator strengths for the lowest 880 levels arising from the 3l3 (0≤l≤2), 3l24l′ (0≤l≤2, 0≤l′≤3), 3s25l (0≤l≤4), 3p25l (0≤l≤1), and 3s3p5l (0≤l≤4) configurations in Al-like Kr XXIV is provided. Comparisons are made with available experimental and theoretical results. Our calculated energies are expected to be accurate enough to facilitate identifications of observed lines involving the n=4,5 levels. The complete data set is also useful for modeling and diagnosing fusion plasma.

27Al MAS NMR Studies of HBEA Zeolite at Low to High Magnetic Fields

27Al single pulse (SP) MAS NMR spectra of HBEA zeolites with high Si/Al ratios of 71 and 75 were obtained at three magnetic field strengths of 7.05, 11.75, and 19.97 T. High field 27Al MAS NMR spectra acquired at 19.97 T show significantly improved spectral resolution, resulting in at least two well-resolved tetrahedral-Al NMR peaks. Based on the results obtained from 27Al MAS and MQMAS NMR acquired at 19.97 T, four different quadrupole peaks are used to deconvolute the 27Al SP MAS spectra acquired at various fields by using the same set of quadrupole coupling constants, asymmetric parameters and relative integrated peak intensities for the tetrahedral Al peaks. The line shapes of individual peaks change from typical quadrupole line shape at low field to essentially symmetrical line shapes at high field. We demonstrate that, for fully hydrated HBEA zeolites, the effect of second-order quadrupole interaction can be ignored, and quantitative spectral analysis can be performed by directly fitting the high fi...

EXTENDED RELATIVISTIC CONFIGURATION INTERACTION AND MANY-BODY PERTURBATION CALCULATIONS OF SPECTROSCOPIC DATA FOR THE N ≤ 6 CONFIGURATIONS IN Ne-LIKE IONS BETWEEN Cr xv AND Kr xxvii

ABSTRACT Level energies, wavelengths, electric dipole, magnetic dipole, electric quadrupole, and magnetic quadrupole transition rates, oscillator strengths, and line strengths from combined relativistic configuration interaction and many-body perturbation calculations are reported for the 201 fine-structure states of the , , , , , , and configurations in all Ne-like ions between Cr xv and Kr xxvii. Calculated level energies and transition data are compared with experiments from the National Institute of Standards and Technology (NIST) and CHIANTI databases, and other recent benchmark calculations. The mean energy difference with the NIST experiments is only 0.05%. The present calculations significantly increase the amount of accurate spectroscopic data for the n > 3 states in a number of Ne-like ions of astrophysical interest. A complete data set should be helpful for analyzing new observations from solar and other astrophysical sources, and is also likely to be useful for modeling and diagnosing a variety of plasmas, including astronomical and fusion plasma.

Mössbauer study of the magnetocaloric compound AlFe2 B 2

Mössbauer spectroscopy in the ferromagnetic AlFe2 B 2 reveals Tc=299 K and shows good agreement with magnetic measurements. The crystals are plate-shaped. The flakes are found from X-ray diffraction to be in the crystallographic ac-plane in the orthorhombic system. The axes of the principle electric field gradient tensor are, by symmetry, colinear with the crystal a-, b- and c-axes. By using information about the quadrupole splitting and line asymmetry in the paramagnetic regime together with the quadrupole shift of the resonance lines in the ferromagnetic regime the magnetic hyperfine field direction is found to be in the ab-plane having an angle =40° to the b-axis.

Dominance of the Breit interaction in the cross section and circular polarization of x-ray radiation following longitudinally-polarized-electron-impact excitation of highly charged ions

Longitudinally-polarized-electron-impact excitation cross sections from the ground state to the individual magnetic sublevels of the excited state $1s2{s}^{2}2{p}_{3/2}$($J = 2$) of highly charged Be-like ions are calculated using a fully relativistic distorted-wave method. The contributions of the Breit interaction to the cross sections and circular polarizations of the $1s2{s}^{2}2{p}_{3/2}$($J = 2$)$\ensuremath{\rightarrow}1{s}^{2}2{s}^{2}$($J = 0$) magnetic quadrupole (M2) line for selected Be-like ${\mathrm{Ag}}^{43+}$, ${\mathrm{Ho}}^{63+}$, and ${\mathrm{Bi}}^{79+}$ ions are investigated systematically. It is found that the Breit interaction has a large effect and makes the cross sections increase, especially to the ${m}_{f}$ = $\ensuremath{-}1$ and $\ensuremath{-}2$ sublevels, the Breit interaction can modify the cross sections by several orders of magnitude. These dramatic influences also lead to a remarkable decrease in the circular polarization of subsequent x-ray radiation, the character of which becomes more and more evident with increasing incident energy and atomic number. And all these characteristics are very different from the conclusions for the linear polarization of radiation following the electron-impact process [S. Fritzsche, A. Surzhykov, and T. St\"ohlker, Phys. Rev. Lett. 103, 113001 (2009); Z. W. Wu, J. Jiang, and C. Z. Dong, Phys. Rev. A 84, 032713 (2011)].

Electric quadrupole transition probabilities and line strengths of Ti11+

Electric quadrupole transition probabilities and line strengths have been calculated using the weakest bound electron potential model for sodium-like titanium, considering many transition arrays. We employed numerical Coulomb approximation and non-relativistic Hartree–Fock wavefunctions for the expectation values of radii in determination of parameters of the model. The necessary energy values have been taken from experimental data in the literature. The calculated electric quadrupole line strengths have been compared with available data in the literature and good agreement has been obtained. Moreover, some electric quadrupole transition probability and line strength values not existing in the literature for some highly excited levels have been obtained using this method.

Polarization of M2 line emitted from highly-charged beryllium-like ions following electron-impact excitation

The contributions of the Breit interaction to the linear polarization of the 1s2s22p3/2 J=2 → 1s22s2 J=0 magnetic quadrupole (M2) line following electron-impact excitation have been investigated systematically for the beryllium isoelectronic sequence with 42 ≤ Z ≤ 92. It is found that the Breit interaction depolarizes significantly the linear polarization of the M2 fluorescence radiation and that these depolarization effects increase as the incident electron energy and/or the atomic number is enlarged.

Intensity of electric quadrupole emission in oxygen investigated by means of a matrix formalism

A matrix formalism is introduced to study the intensity of electric quadrupole emission in oxygen. In fact, the total intensity of the electric quadrupole lines in the above emission is expressed in terms of matrices with full physical meaning whose main aspects are discussed.

Correlated ligand dynamics in oxyiron picket fence porphyrins: structural and Mössbauer investigations.

Disorder in the position of the dioxygen ligand is a well-known problem in dioxygen complexes and, in particular, those of picket fence porphyrin species. The dynamics of Fe-O2 rotation and tert-butyl motion in three different picket fence porphyrin derivatives has been studied by a combination of multitemperature X-ray structural studies and Mössbauer spectroscopy. Structural studies show that the motions of the dioxygen ligand also require motions of the protecting pickets of the ligand binding pocket. The two motions appear to be correlated, and the temperature-dependent change in the O2 occupancies cannot be governed by a simple Boltzmann distribution. The three [Fe(TpivPP)(RIm)(O2)] derivatives studied have RIm = 1-methyl-, 1-ethyl-, or 2-methylimidazole. In all three species there is a preferred orientation of the Fe-O2 moiety with respect to the trans imidazole ligand and the population of this orientation increases with decreasing temperature. In the 1-MeIm and 1-EtIm species the Fe-O2 unit is approximately perpendicular to the imidazole plane, whereas in the 2-MeHIm species the Fe-O2 unit is approximately parallel. This reflects the low energy required for rotation of the Fe-O2 unit and the small energy differences in populating the possible pocket quadrants. All dioxygen complexes have a crystallographically required 2-fold axis of symmetry that limits the accuracy of the determined Fe-O2 geometry. However, the 80 K structure of the 2-MeHIm derivative allowed for resolution of the two bonded oxygen atom positions and provided the best geometric description for the Fe-O2 unit. The values determined are Fe-O = 1.811(5) Å, Fe-O-O = 118.2(9)°, O-O = 1.281(12) Å, and an off-axis tilt of 6.2°. Demonstration of the off-axis tilt is a first. We present detailed temperature-dependent simulations of the Mössbauer spectra that model the changing value of the quadrupole splitting and line widths. Residuals to fits are poorer at higher temperature. We believe that this is consistent with the idea that population of the two conformers is related to the concomitant motions of both Fe-O2 rotations and motions of the protecting tert-butyl pickets.

Polarization of M2 Line Emitted Following Electron-Impact Excitation of Beryllium-Like Ions

Detailed calculations are carried out for the electron-impact excitation cross sections from the ground state to the individual magnetic sublevels of the 1s2s22p3/2J = 2 excited state of highly-charged beryllium-like ions by using a fully relativistic distorted-wave (RDW) method. The contributions of the Breit interaction to the linear polarization of the 1s2s22p3/2 J = 2 →1s22s2 J = 0 magnetic quadrupole (M2) line are investigated systematically for the beryllium isoelectronic sequence with 42 ≤ Z ≤ 92. It is found that the Breit interaction depolarizes significantly the linear polarization of the M2 fluorescence radiation and that these depolarization effects increase as the incident electron energy and/or the atomic number is enlarged.

Determination of Chlorinated-and Brominated-Polycyclic Aromatic Hydrocarbons in Soil Samples by Gas Chromatography Coupled with Triple Quadrupole Mass Spectrometry

In this study,simultaneous determination of Cl-PAHs and Br-PAHs was developed by gas chromatography coupled to triple quadrupole mass spectrometry( GC-QQQ-MS/MS).Soil samples were exacted and cleaned through silica gel column,dual-layer carbon reversible column respectively,after that,19 congeners of Cl-PAHs and 8 congeners of Br-PAHs were quantified.The GC-QQQ-MS/MS analysis condition was: EI and Multi-reaction monitoring( MRM) model,the electron emission energy was 70 eV;DB-5 MS fused silica capillary column( 60 m×0.25 mm,0.25 μm); the temperatures of injection,ion source,quadrupole and transfer line were 280,230,150 and 300 ℃,respectively.The collision and quenching flow were 1.5 and 2.25 mL/min,respectively.The carrier gas was Helium with the flow1.0 mL/min.The results showed that the relative standard deviation( RSD) of parallel standard reference sample were ≤12.0%,and the recoveries of d-PAHs,Cl-PAHs and Br-PAHs were between 70%-118%.The instrument detection limits of Cl-PAHs and Br-PAHs were between 0.4-5.0 pg.Concentrations of∑Cl-PAHs and ∑Br-PAHs in the soil samples from a certain industrial area were in the range of 725-1012 pg/g and 353-5924 pg/g,respectively.

Radiative transfer effects during primordial helium recombination

In this paper we refine the calculation of primordial helium recombination, accounting for several additional effects that were neglected or treated more approximately in previous studies. These include consideration of the following: (i) time-dependent radiative transfer interaction between the 21P1–11S0 and 23P1–11S0 resonances; (ii) time-dependent radiative transfer for the partially overlapping n1P1–11S0, n1D2–11S0 and n3P1–11S0 series with 3 ≤n≤ 10; (iii) electron scattering within a kernel approach. We also briefly discuss the effect of electron scattering and H i quadrupole lines on the recombination of hydrogen. Although the physics of all considered processes is interesting and subtle, for the standard cosmology, with helium abundance Yp≃ 0.24, the overall correction to the ionization history during helium recombination with respect to the previous implementation of CosmoRec remains smaller than |ΔNe/Ne| ≃ 0.05 per cent. The dominant improvement is caused by consistent inclusion of resonance scattering for the 21P1–11S0 resonance. For cosmologies with a large helium fraction, Yp≃ 0.4, the difference reaches |ΔNe/Ne| ≃ 0.22 per cent at z≃ 1800; however, the overall correction to the cosmic microwave background power spectra is small, exceeding |ΔCl/Cl| ≃ 0.05 per cent only at l≳ 3000. In comparison to the current version of Recfast the difference reaches |ΔCl/Cl| ≃ 0.4 per cent at l≃ 3000 for Yp≃ 0.4, and also for the standard value Yp≃ 0.24 we find differences of |ΔCl/Cl| ≳ 0.1 per cent at l≃ 2500. The new processes are now included by the cosmological recombination code CosmoRec and can be activated as needed for most settings without affecting its runtime significantly.

Anisotropic mean-squared-displacement tensor in cubic almandine garnet: a single crystal 57Fe Mössbauer study

This paper describes single-crystal measurements on a crystal plate cut from a naturally-occurring almandine-rich single crystal (Alm69Pyr19Spe8Gro4) from Wrangell Alaska. The objective was to measure the mean-squared-displacement (msd) tensor precisely using Mossbauer spectroscopy. Parallel quantum-mechanical calculations based on X-ray determined atomic displacement parameters and Mossbauer parameters from polycrystalline measurements indicated that the msd tensor should display significant anisotropy, easily measurable within the precision of the Mossbauer experiment. For each single-crystal orientation the observed Mossbauer spectrum represents a macroscopic quantity that is the average over six symmetry-related (local) dodecahedral sites in which the high-spin Fe2+ ions reside. The anisotropy in the measured msd tensor is, nevertheless, unequivocal. Furthermore, the magnitudes of the Mossbauer-determined msd principal values exceed those of the corresponding X-ray-determined quantities by a factor 3.7. The equivalent recoilless fractions are also anisotropic and consequently one observes the Gol’danskii–Karyagin Effect (GKE), as manifested by an asymmetric quadrupole doublet in polycrystalline absorbers. Moreover, the line widths of the two quadrupole lines are markedly different but angle invariant. This is interpreted as implying that, in addition to anisotropy in the msd tensor, differential spin–spin relaxation is present in the \( m = \pm 3/2 \leftrightarrow \pm 1/2 \) and \( m = \pm 1/2 \leftrightarrow \pm 1/2,\, \mp 1/2 \) nuclear transitions. While both effects contribute to the quadrupole asymmetries observed in Mossbauer spectra of polycrystalline almandine, the GKE is apparently predominant.