Isotopic Splitting Research Articles

Molecules in Cool Stars: The A2Π − X2Σ+ and the B2Σ+ − X2Σ+ Band Systems of CaCl

Cool red giant stars exhibit absorption bands of calcium monochloride (CaCl) in the optical region. In this work, the bands of CaCl corresponding to the A2Π − X2Σ+ transition with v′≤ 4 and v″ ≤ 4, and B2Σ+ − X2Σ+ transition with v′≤ 2 and v″ ≤ 2 are rotationally analyzed with PGOPHER, a multipurpose program for simulating and fitting molecular spectra. All bands were analyzed using high-resolution absorption spectra collected at the National Solar Observatory in 1985, calibrated with atomic lines from a high-resolution emission spectrum obtained in a separate hollow cathode experiment. The results are compared with previous laser-induced fluorescence measurements. Overall, the accuracy of spectroscopic constants for the A2Π and B2Σ+ states is improved. Scaled transition dipole moment calculations were used to obtain line strengths. Line lists are provided with Einstein A coefficients and oscillator strengths, which can be used to determine CaCl stellar abundances. Additionally, isotope splittings allowed us to estimate band origins for the 40Ca37Cl isotopologue based on band-head positions.

Isotopic analysis of uranium at the picogram level with single-shot laser induced breakdown spectroscopy

Uranium was measured by laser induced breakdown spectroscopy (LIBS) with a limit of detection of 1.3 picograms with spectral-peak height as the analytical parameter, which shows an improvement of several orders of magnitude compared to other reports in the literature. The improvement is a result of optimizing the choice of the U analytical line, the system hardware, and the light collection and detection efficiency. The research established properties of U line emission (intensity, signal-to-background ratio, isotopic splitting, and spectral interferences) to select an optimum wavelength for analysis. The samples were mock particles from dried, monodispersed U solution droplets (∼65 pL in volume) deposited on Si wafers. LIBS emission spectra from several 235U-enriched samples were measured to demonstrate the performance for isotopic analysis. For isotopic measurements, two masses for total U, 100 pg and 325 pg, were studied. The 235U: 238U isotopic ratio was obtained by peak fitting the LIBS spectra without requiring calibration with the use of enriched standards. Depending on the total U mass and the 235U enrichment, typical relative standard deviations of the isotopic analysis ranged from several percent down to about 1%. Further, the developed method and the reported analytical performance were all based on single-shot LIBS. Overall, the study highlights the potential of LIBS as a robust and sensitive technique for isotopic analysis of U-containing particles.

Conformational adaptation and large amplitude motions of 1-phenyl-2,2,2-trifluoroethanol with two water molecules: a rotational spectroscopic and ab initio investigation.

The 1 : 2 adduct of 1-phenyl-2,2,2-trifluoroethanol (PhTFE), a chiral fluoroalcohol, with two water molecules (PhTFE⋯2H2O) was investigated via chirped pulse Fourier-transform microwave (CP-FTMW) spectroscopy and theoretical calculations. A systematic search of the PhTFE⋯2H2O conformational landscape identified 38 stable minima at the B3LYP-D3BJ/def2-TZVPPD level of theory, 27 of which are within an energy window of 10 kJ mol-1 after applying zero-point energy corrections. Rotational spectra of a single PhTFE⋯2H2O conformer along with eight deuterated and three oxygen-18 isotopologues were assigned. Interestingly, the observed PhTFE⋯2H2O conformer contains PhTFE II, the second most stable monomer conformer, and the most stable PhTFE I dihydrate is ca. 4 kJ mol-1 higher in energy. In contrast, PhTFE I⋯H2O was identified experimentally and theoretically as the most stable 1 : 1 conformer. Furthermore, the observed dihydrate structure experiences large amplitude motions connecting three theoretical minima which differ only in which water oxygen lone pairs are involved in the hydrogen-bonds, i.e., the free OH pointing directions. Additionally, the ortho and para-H2O tunnelling splittings were detected and attributed to the interchange water hydrogen atoms which interact with the aromatic part of PhTFE but not for the water interacting with PhTFE hydroxy group. Extensive theoretical modelling was carried out to gain insight into the associated large amplitude motions including tunnelling, supported by the experimental isotopic and tunnelling splitting data.

Spectra of Rg-water dimers in the region of the D2O ν3 asymmetric stretch (Rg = Ar, Kr, Xe)

Spectra of rare gas (Rg) – D2O dimers (Rg = Ar, Kr, Xe) are studied in the region of the D2O ν3 asymmetric stretch (≈2800 cm−1), using a rapid-scan tunable infrared optical parametric oscillator source to probe a pulsed supersonic slit jet expansion. Three bands are observed in each case, labelled according to the D2O rotational transition with which they correlate as: Σ(101) ← Σ(000), Π(101) ← Σ(000), and Σ(000) ← Σ(101). The Ar-D2O bands exhibit various perturbations and line broadening effects. For Kr-D2O, the Π(101) ← Σ(000) and Σ(000) ← Σ(101) bands are simple and relatively unperturbed with almost no resolved Kr isotope structure, while the Σ(101) ← Σ(000) band is highly perturbed and shows large isotope splittings. This latter perturbation is analyzed in detail with good results. For Xe-D2O, the experimental spectra are unfortunately weaker. Analysis of the Π(101) ← Σ(000) and Σ(000) ← Σ(101) bands is again relatively straightforward, but the Σ(101) ← Σ(000) band is even more perturbed than for Kr-D2O and its analysis proves impossible. Line broadening (for Ar-D2O) and vibrational frequency shift effects are described.

Spectra of CO2‐Kr in the 4.3 μm region: Intermolecular Bend and Symmetry Breaking of the Intramolecular CO2 Bend

AbstractThe infrared spectrum of CO2‐Kr complex is studied in the region of the carbon dioxide ν3 fundamental vibration (≈2350 cm−1). Tunable IR radiation from an OPO is employed to record absorption spectrum of the complex generated in a pulsed supersonic slit jet. The spectrum exhibits broadening and splitting of transitions due to mass dependence of the five Kr isotopes with natural abundances exceeding 2 %. Good simulation of the spectrum is achieved by scaling the vibrational and rotational parameters. This scaling model is particularly important for the combination band involving the intermolecular bending mode where many isotope splittings are observed. As with other CO2‐rare gas complexes, we also observe weak hot bands of CO2‐Kr transitions corresponding to the hot band originating in the CO2 intramolecular bend. From these we determine a splitting of 1.418 cm−1 between the in‐plane and out‐of‐plane bend of CO2, due to the neighboring Kr atom.

N2O–Ar and N2O–Kr: Intermolecular vibrations of N2O–Kr and symmetry breaking of the N2O bending mode in the presence of a rare gas

Rotationally-resolved infrared spectra of N2O–Ar and N2O–Kr are studied in the region of the N2O ν1 vibration (≈2224 cm−1) using a tunable Quantum Cascade laser source to probe a pulsed supersonic jet. The N2O–Kr ν1 fundamental band is re-analyzed, together with previous ν3 band data, using a unified scheme to fit the (small) observed Kr isotope splittings. This scheme is then transferred to analyze the bending combination band of N2O–Kr near 2257 cm−1 where isotope effects are much larger due to stretch-bend interactions. As a result, N2O–Kr intermolecular bend (33.29 cm−1) and stretch (34.48 cm−1) frequencies are directly determined for the first time. Weak spectra are detected for both N2O–Ar and –Kr corresponding to the (ν1, ν2l2, ν3) = (1110) ← (0110) hot band of N2O. Their analysis yields the magnitude of the splitting of the N2O ν2 bending mode into in-plane and out-of-plane components. These splittings are found to be significantly smaller than those observed in the analogous CO2-containing dimers.

Atomic data for the Gaia-ESO Survey

Context. We describe the atomic and molecular data that were used for the abundance analyses of FGK-type stars carried out within the Gaia-ESO Public Spectroscopic Survey in the years 2012 to 2019. The Gaia-ESO Survey is one among several current and future stellar spectroscopic surveys producing abundances for Milky-Way stars on an industrial scale. Aims. We present an unprecedented effort to create a homogeneous common line list, which was used by several abundance analysis groups using different radiative transfer codes to calculate synthetic spectra and equivalent widths. The atomic data are accompanied by quality indicators and detailed references to the sources. The atomic and molecular data are made publicly available at the CDS. Methods. In general, experimental transition probabilities were preferred but theoretical values were also used. Astrophysical gf-values were avoided due to the model-dependence of such a procedure. For elements whose lines are significantly affected by a hyperfine structure or isotopic splitting, a concerted effort has been made to collate the necessary data for the individual line components. Synthetic stellar spectra calculated for the Sun and Arcturus were used to assess the blending properties of the lines. We also performed adetailed investigation of available data for line broadening due to collisions with neutral hydrogen atoms. Results. Among a subset of over 1300 lines of 35 elements in the wavelength ranges from 475 to 685 nm and from 850 to 895 nm, we identified about 200 lines of 24 species which have accurate gf-values and are free of blends in the spectra of the Sun and Arcturus. For the broadening due to collisions with neutral hydrogen, we recommend data based on Anstee-Barklem-O’Mara theory, where possible. We recommend avoiding lines of neutral species for which these are not available. Theoretical broadening data by R.L. Kurucz should be used for Sc II, Ti II, and Y II lines; additionally, for ionised rare-earth species, the Unsöld approximation with an enhancement factor of 1.5 for the line width can be used. Conclusions. The line list has proven to be a useful tool for abundance determinations based on the spectra obtained within the Gaia-ESO Survey, as well as other spectroscopic projects. Accuracies below 0.2 dex are regularly achieved, where part of the uncertainties are due to differences in the employed analysis methods. Desirable improvements in atomic data were identified for a number of species, most importantly Al I, S I, and Cr II, but also Na I, Si I, Ca II, and Ni I.

FTIR spectroscopy of adsorbed ozone

FTIR spectra of ozone adsorbed at 77 K on a number of oxide adsorbents were investigated. Special attention was paid to the position and isotopic splitting of the band of ν1+3 combination vibration. For titania eight distinct bands were distinguished and put in correspondence with the bands of ν1 and ν3 vibrations. Chemisorption is accompanied by the frequency increase of the combination band mostly at the expense of decreased anharmonicity. Besides TiO2 and CeO2, ozone chemisorption with the blue shifted ν1+3 band was found for BeO and some cation-exchanged zeolites, while for Al2O3 and ZnO only physisorbed molecules were detected.

Fine structures in Raman spectra of tetrahedral tetrachloride molecules in femtosecond coherent spectroscopy.

Herewith, we present fast Fourier transforms of time resolved signals, obtained by use of the femtosecond transient transmission (TT) spectroscopy, for three tetrachlorides, CCl4, SiCl4, and GeCl4, and chloroform, CHCl3. Due to coherent excitation of molecules, the isotopic splitting of their spectral bands in the range of symmetric stretching vibration can be observed with high resolution not available in spontaneous Raman scattering. The intensity distribution in the isotopic fine structure pattern appears to differ for various studied molecules, which is explained by the role of intermolecular interactions and the local order of molecules in the liquids. In particular, in SiCl4, the vibrational band exhibits anomalous ratios of the peak amplitudes, which do not agree with the natural abundance of the isotopologues. Using the simple oscillatory model of the liquid and fitting theoretical curves to the experimental results, we have been able to find the intermolecular force constants for all three liquids and to formulate the conclusion that the anomalous spectral pattern in SiCl4 results from strong interactions between the closest Cl atoms belonging to adjacent molecules. Application of the windowed Fourier transform enables us to study the dynamics of intermolecular interactions. The strength of intermolecular interactions in CCl4, SiCl4, and GeCl4, found by the TT technique, is compared with the results obtained by means of the femtosecond optical Kerr effect spectroscopy.

Dual-comb spectroscopy of laser-induced plasmas

Dual-comb spectroscopy has become a powerful spectroscopic technique in applications that rely on its broad spectral coverage combined with high frequency resolution capabilities. Experiments to date have primarily focused on detection and analysis of multiple gas species under semi-static conditions, with applications ranging from environmental monitoring of greenhouse gases to high-resolution molecular spectroscopy. Here, we utilize dual-comb spectroscopy to demonstrate broadband, high-resolution, and time-resolved measurements in a laser-induced plasma. As a demonstration, we simultaneously detect trace amounts of Rb and K in solid samples with a single laser ablation shot, with transitions separated by over 6 THz (13 nm) and spectral resolution sufficient to resolve isotopic and ground state hyperfine splittings of the Rb D2 line. This new spectroscopic approach offers the broad spectral coverage found in the powerful techniques of laser-induced breakdown spectroscopy (LIBS) while providing the high-resolution and accuracy of cw laser-based spectroscopies.

Formation and identification of borane radical anions isolated in solid argon.

The infrared (IR) spectrum of borane(3) anions (BH3-) isolated in solid Ar was recorded; two vibrational modes were observed at 2259.4 and 606.6 cm-1, which were assigned to the BH2 stretching (ν3) and out-of-plane large-amplitude (ν2) modes, respectively. These anions were produced by the electron bombardment of an Ar matrix sample containing a small proportion of B2H6 and H2 during matrix deposition or by the photolysis of single-bridged-B2H5- in an Ar matrix with the selected ultraviolet light. The band positions, relative intensity ratios, isotopic splitting pattern, and isotopic shift ratios of the observed IR features of BH3- are generally in good agreement with those predicted by the B2PLYP/aug-cc-pVTZ method.

Paper spray and Kendrick mass defect analysis of block and random ethylene oxide/propylene oxide copolymers

Paper spray ionization coupled with a high-resolution time-of-flight mass spectrometer was applied to the analysis of 13 block and 2 random ethylene oxide/propylene oxide (EO/PO) copolymers as well as to standard samples of poly(ethylene oxide) and poly(propylene oxide) homopolymers. Paper spray mass spectra could be obtained rapidly and, unlike electrospray ionization, were not subject to contamination and sample carryover. For comparison, polyether samples were also measured on a MALDI/TOF system with ultrahigh mass resolving power. MALDI/high-resolution time-of-flight mass spectrometry exhibited single-charge ions characteristic of the polymer distributions whereas the paper spray mass spectra exhibited charge states ranging from one to six charges. Kendrick mass defect plots of the multiple-charge ions in the paper spray mass spectra exhibit isotopic splitting of the Kendrick mass defects, facilitating visualization of the number of charges in each series. The slope of the KMD plots can be used to estimate the percentage of ethylene oxide in the copolymers. In-source fragmentation permitted the distinction between block and random copolymers.

Synthesis, Crystal Structure, and Properties of Bi3 TeBO9 or Bi3 (TeO6 )(BO3 ): A Non-Centrosymmetric Borate-Tellurate(VI) of Bismuth.

Pale-yellow single crystals of the new borate tellurate(VI) Bi3 TeBO9 were obtained by reaction of stoichiometric amounts of Bi2 O3 , B2 O3 , and Te(OH)6 at 780 °C. The non-centrosymmetric crystal structure (P63 , Z=2, a=8.7454(16), c=5.8911(11) Å, 738 refl., 43 param, R1=0.037, wR2=0.093) contains isolated trigonal-planar BO3 units and nearly undistorted TeO6 octahedra. The Bi3+ cations are located in between in octahedral voids. The BiO6 octahedra are significantly distorted to a [3+3] pattern (2.25/2.50 Å) due to the ns2 configuration. According to the structural features, the formula can be written as Bi3 (TeO6 )(BO3 ). Alternatively, the structure can also be described as hcp of oxygen with TeVI and BiIII in octahedral voids and BIII in trigonal- planar voids. The vibrational spectra show the typical features of BO3 and TeO6 units with a significant 10 B/11 B isotopic splitting of the IR-active B-O valence mode (1248 and 1282 cm-1 ). The UV/Vis spectrum shows an optical band edge with an onset around 480 nm (2.6 eV). MAS-NMR spectra of 11 B show an anisotropic signal with a quadrupole coupling constant of CQ =2.55 MHz. and a very small deviation from rotational symmetry (η=0.2). The isotropic chemical shift is 20.1 ppm. The second harmonic generation (SHG) test was positive with an activity comparable to potassium dihydrogen phosphate (KDP). Bi3 TeBO9 decomposes in air at 825 °C to Bi2 TeO5 .

Isotopic determination of uranium in soil by laser induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) operated under ambient pressure has been evaluated for isotopic analysis of uranium in real-world samples such as soil, with U concentrations in the single digit percentage levels. The study addresses the requirements for spectral decomposition of 235U and 238U atomic emission peaks that are only partially resolved. Although non-linear least-square fitting algorithms are typically able to locate the optimal combination of fitting parameters that best describes the experimental spectrum even when all fitting parameters are treated as free independent variables, the analytical results of such an unconstrained free-parameter approach are ambiguous. In this work, five spectral decomposition algorithms were examined, with different known physical properties (e.g., isotopic splitting, hyperfine structure) of the spectral lines sequentially incorporated into the candidate algorithms as constraints. It was found that incorporation of such spectral-line constraints into the decomposition algorithm is essential for the best isotopic analysis. The isotopic abundance of 235U was determined from a simple two-component Lorentzian fit on the U II 424.437nm spectral profile. For six replicate measurements, each with only fifteen laser shots, on a soil sample with U concentration at 1.1% w/w, the determined 235U isotopic abundance was (64.6±4.8)%, and agreed well with the certified value of 64.4%. Another studied U line – U I 682.691nm possesses hyperfine structure that is comparatively broad and at a significant fraction as the isotopic shift. Thus, 235U isotopic analysis with this U I line was performed with spectral decomposition involving individual hyperfine components. For the soil sample with 1.1% w/w U, the determined 235U isotopic abundance was (60.9±2.0)%, which exhibited a relative bias about 6% from the certified value. The bias was attributed to the spectral resolution of our measurement system – the measured line width for this U I line was larger than its isotopic splitting. Although not the best emission line for isotopic analysis, this U I emission line is sensitive for element analysis with a detection limit of 500ppmU in the soil matrix; the detection limit for the U II 424.437nm line was 2000ppm.

Diagnostics of horizontal velocity field in the solar atmosphere: Line Ba II λ 455.403 nm

We proposed a method for diagnostics of the horizontal velocity field based on 2D observations at the center of the solar disk with high spatial and temporal resolution. The method consists in semiempirical modeling of the solar atmosphere by solving the inverse radiative transfer problem and subsequent obtaining horizontal velocities by solution of the corresponding hydrodynamic equations. We investigated the diagnostic capabilities of the line Ba II λ 455.403 nm (considering hyperfine structure and isotope splitting) for studying the horizontal velocity field of the nonhomogeneous solar atmosphere.

Spectral characteristics of gas discharge ion lasers on vapors of thallium and gallium

The results of calculation and measurements of the hyperfine and isotopic structure splitting of laser lines of thallium ion (?594.9 nm and ?695 nm TlII) and gallium ion (?633.4 nm GaII) are presented. That is caused by hyperfine splitting of upper and lower laser levels on some sublevels, and also by the shift of sublevels energy taking place because of volume isotopic effect for different isotopes which are present in the natural mixture of each metal.

Isotopic splitting patterns in the (13) C NMR spectra of some partially deuterated 1-aryl-2-(phenyldiazenyl)butane-1,3-dione and 4-hydroxy-3-(phenyldiazenyl)-2H-chromen-2-one: evidence for elucidation of tautomeric forms.

Nuclear magnetic resonance spectra of synthesized azo dyes derived from aniline derivatives in reaction with benzoylacetone and 4-hydroxycoumarin were studied in both CDCl3 and (CD3 )2 SO (two drops of D2 O were added into solutions of dyes). All dyes showed intramolecular hydrogen bonding. Dyes derived from o-nitro aniline in the reaction with benzoylacetone, and 4-hydroxycoumarin showed bifurcated intramolecular hydrogen bonds. The solvent-substrate proton exchange of dyes derived from benzoylacetone and 4-hydroxycoumarin was examined in the presence of two drops of D2 O. Among ten dye samples, two dyes derived from benzoylacetone did not show deuteration, three dyes showed partial deuteration and five dyes showed full deuteration under similar conditions. For the partially deuterated dyes the β-isotope effect in (13) C splitting was investigated and was used for the determination of the predominant tautomeric form.

Diagnostics of the solar atmosphere by the Non-LTE inversion method: Line of Ba II λ 455.403 nm

The inverse problem of nonequilibrium radiative transfer in the Ba II λ 455.403 nm line is solved taking into account the hyperfine structure and isotopic splitting. Diagnostic capabilities of this line for the study of the solar atmosphere are investigated based on the three-dimensional hydrodynamic model. It is shown that the use of inversion methods for the analysis of the observed Ba II λ 455.403 nm line makes it possible to reproduce physical conditions in the layers of the photosphere and the lower chromosphere (0 < h < 600 km) with a correlation coefficient of 0.9.

MPCVD growth of 13C-enriched diamond single crystals with nitrogen addition

This study describes the growth of 13C-enriched (100)-oriented diamond single crystals by the MPCVD (microwave plasma chemical vapour deposition) process. All crystals are at least 6×6mm2 in area and 0.5–1.0mm in thickness. The samples with nominal 13C percentages (R=[13C]/[13C+12C]) of 0.011 (natural abundance), 0.10, 0.21, 0.24 and 0.34 were obtained by controlling the flow of the carbon-13 and carbon-12 methane feed gases. To obtain thicker and near-colourless quality 13C-enriched diamond, 190ppm of nitrogen was added into the gas mixture. The shift towards lower frequency in the Raman peak positions and decrease in the thermal conductivities of the near-colourless crystals with increasing 13C percentages are similar to previous studies of isotopically-controlled diamond grown with no nitrogen additive. The images of the structural defects associated with 13C-enrichment obtained by spatially-resolved X-ray rocking curve measurement show distinct patterned structures that runs parallel to the <100> direction. Moreover, the broadening in the line width of the nuclear magnetic resonance (NMR) peak from sp313C correlates with increasing R. We also expand the study by injecting 500ppm of nitrogen. Higher nitrogen concentration leads to the formation of brown crystals. The brown crystals show far greater 13C NMR peak intensity than the near-colourless. This suggests that paramagnetic nitrogen impurities in the brown crystals hasten the spin-lattice relaxation time of the 13C nuclear spin that resulted in higher intensity. The isotopic splitting observed for the localized vibrational mode of the NVH0 defect in brown crystals is attributed to the co-existence of both the 13C (3114.2cm−1) and 12C (3123.5cm−1). Unlike the isotopic splitting observed for NVH0 defect, the peak position of the Ns+ defect shifts towards lower frequency as R increases. Not only have we demonstrate the growth of bigger isotopically-controlled diamond single crystals, the results shown here have provided a framework to further investigate the interplay between 13C atoms and nitrogen impurity.

Diffusional Separation of Calcium Isotopes in Chemically Peculiar Stellar Atmospheres

Abstract Diffusional separation of calcium isotopes in the atmospheres of hot chemically peculiar stars is studied. In addition to the usual radiative acceleration effect, the light-induced drift is taken into account. We propose that microturbulence in stable stellar atmospheres is generated by the interaction between plasma particles and radiative flux. Formulae for the microturbulent velocity and microturbulence diffusion coefficient are derived. Data on isotopic and hyperfine splitting of the calcium spectral lines have been collected as an input file. The equilibrium Ca isotope concentrations are found in model computations, iteratively correcting the radiative acceleration values. The general picture of Ca isotope stratification is found to be similar to our previous results obtained for Hg isotopes: dominating overabundance of the heaviest isotope. Diffusional stratification of Ca isotope concentrations in atmospheres of late B and early A spectral types are computed and visualized in figures. The isotope abundances on the inner boundary surface were fixed to be the solar ones. The computed Ca II infrared triplet line profiles are compared with the observed line profiles in a high-dispersion spectrum of HD 175640.