Rare Isotopologues Research Articles

MARVEL analysis of high-resolution rovibrational spectra of the 18O12C18O, 17O12C18O, and 18O13C18O isotopologues of carbon dioxide

For three rare isotopologues of carbon dioxide, 18O12C18O (828, according to a well-established shorthand notation), 17O12C18O (728), and 18O13C18O (838), 3923, 4318, and 1058 empirical rovibrational energy levels, respectively, are determined, using the MARVEL (Measured Active Rotational–Vibrational Energy Levels) protocol and code. For the isotopologues 828/728/838, the analysis of their spectroscopic network is based on 11353(7665)/11313(7700)/2155(1595) measured(unique) transitions, belonging to 165/113/50 vibrational bands, respectively. The measured transitions collected from the literature span the regions 953–12570 cm−1 (for 828), 628–8197 cm−1 (for 728), and 600–7918 cm−1 (for 838). The number of critically evaluated and recommended energy levels of this study are 3923, 4318, and 1058 for the 828, 728, and 838 isotopologues of CO2, respectively. Comparison of the empirical rovibrational energy levels determined in this study with their counterparts in two published databases, CDSD-2019, Ames-2021 and HITRAN shows very good overall agreement.

Interstellar Nitrogen Isotope Ratios: Measurements on Tracers of C14N and C15N

The nitrogen isotope ratio 14N/15N is a powerful tool to trace Galactic stellar nucleosynthesis and constrain Galactic chemical evolution. Previous observations have found lower 14N/15N ratios in the Galactic center and higher values in the Galactic disk. This is consistent with the inside-out formation scenario of our Milky Way. However, previous studies mostly utilized double isotope ratios also including 12C/13C, which introduces additional uncertainties. Here we present observations of C14N and its rare isotopologue, C15N, toward a sample of star-forming regions measured by the IRAM 30 m and/or the ARO 12 m telescope at λ ∼ 3 mm wavelength. For those 35 sources detected in both isotopologues, physical parameters are determined. Furthermore, we have obtained nitrogen isotope ratios using the strongest hyperfine components of CN and C15N. For those sources showing small deviations from local thermodynamical equilibrium and/or self-absorption, the weakest hyperfine component, likely free of the latter effect, was used to obtain reliable 14N/15N values. Our measured 14N/15N isotope ratios from C14N and C15N measurements are compatible with those from our earlier measurements of NH3 and 15NH3 (Paper I), i.e., increasing ratios to a Galactocentric distance of ∼9 kpc. The unweighted second-order polynomial fit yields C14NC15N=(−4.85±1.89)kpc−2×RGC2+(82.11±31.93)kpc−1×RGC−(28.12±126.62) . Toward the outer galaxy, the isotope ratio tends to decrease, supporting an earlier finding by H13CN/HC15N. Galactic chemical evolution models are consistent with our measurements of the 14N/15N isotope ratio, i.e., a rising trend from the Galactic center region to approximately 9 kpc, followed by a decreasing trend with increasing R GC toward the outer Galaxy.

FT-spectroscopy of the 12C18O rare isotopologue and deperturbation analysis of the A1Π(v = 3) level

Research on 12C18O was carried out using two complementary Fourier-transform methods: (1) vacuum-ultraviolet absorption spectroscopy, with an accuracy ca. 0.03 cm−1 on the DESIRS beamline (SOLEIL synchrotron) and (2) visible emission spectroscopy with an accuracy of about 0.005–0.007 cm−1 by means of the Bruker IFS 125HR spectrometer (University of Rzeszów). The maximum rotational quantum number of the energy levels involved in the observed spectral lines was Jmax = 54. An effective Hamiltonian and the term-value fitting approach were implemented for the precise analysis of the A1Π(v = 3) level in 12C18O. It was performed by means of the PGOPHER code. The data set consisted of 571 spectral lines belonging to the A1Π-X1Σ+(3, 0), B1Σ+-A1Π(0, 3), C1Σ+-A1Π(0, 3) bands and several lines involving states that perturb the A1Π(v = 3) level as well as to the previously analysed B1Σ+-X1Σ+(0, 0) and C1Σ+-X1Σ+(0, 0) transitions. A significantly extended quantum–mechanical description of the A1Π(v = 3) level in 12C18O was provided. It consists of the 5 new unimolecular interactions of the spin–orbit and rotation-electronic nature, which had not been taken into account previously in the literature. The ro-vibronic term values of the A1Π(v = 3, Jmax = 55), aʹ3Σ+(v = 13), D1Δ(v = 4) and I1Σ–(v = 5) levels were determined with precision improved by a factor of 10 relative to the previously known values.

Mass‐correlated rotational Raman spectra and the structure of furan

AbstractWe present mass‐correlated rotational alignment spectroscopy and the first high‐resolution rotational Raman spectra for furan. Spectra were measured with a spectral range up to 0.5 THz and a resolution down to 1.6 MHz. Spectra for 13C and 18O isotopologues were observed in their corresponding mass channels at natural abundance. Based on our data and literature constants, we performed a purely experimental structure analysis for the effective and equilibrium structures of furan. The results highlight the utility of CRASY to obtain rare isotopologue spectra without isotopically enriched samples.

Application of an absolute reference frame for methane clumped-isotope analyses

Clumped-isotope analysis provides new constraints on the formation and evolution of methane. High-resolution isotope-ratio mass spectrometry (HR-IRMS) is a sensitive, precise, and stable analytical technique increasingly used in methane clumped-isotope analysis. However, the lack of standard reference frames hinders the comparison of data from different laboratories and the evaluation of accuracy. In this study, an absolute reference frame was introduced for HR-IRMS analysis of the multiply substituted methane isotopologues 13CH3D and 12CH2D2. We evaluated the optimized performance of a Panorama (Nu Instruments, UK) HR-IRMS system by repeated analysis of an intra-laboratory standard gas, finding that these rare isotopologues can be analyzed separately with high precision, repeatability, and reproducibility. Internal precision (a key parameter in instrument performance) reached 0.15‰ − 0.25‰ for Δ13CH3D and 0.70‰ − 0.85‰ for Δ12CH2D2 values, ensuring the reliability of data. Comparison of results before and after purification demonstrated that purification procedures caused negligible isotopic fractionation of clumped isotopes. Isotopic-exchange experiments revealed source effects in the MS ion source, depending on the difference in bulk H isotopic composition between sample and reference gas, but independent of bulk C isotopic composition. To improve analytical accuracy for methane isotopologues, an absolute reference frame was developed through experiments involving a suite of mixed gases of different H isotopic composition equilibrated at 100 °C and a standard gas equilibrated at 2 °C–500 °C. Based on the reference frame, raw data were processed with a non-linearity correction and converted to real values with empirical transformation functions. The reference frame was applied to analyses of two methane standard gases and three natural gases from Tarim Basin, China. Measured Δ13CH3D and Δ12CH2D2 values for two standard gases were consistent with published values. Clumped-isotope signatures of natural gases preserve information related to the formation temperature of methane.

Rotational conformers and nuclear spin isomers of carbonyl diisothiocyanate.

Nuclear spin isomers of molecules play a pivotal role in our understanding of quantum mechanics and can have significant implications for various fields. In this work, we report the isolation and characterization of stable nuclear spin isomers as well as conformational isomers of a reactive compound, namely carbonyl diisothiocyanate. It can exist as three rotational conformers, two of which, the syn-syn and syn-anti, were observed in a pulsed supersonic jet by chirped pulse Fourier transform microwave spectroscopy in the 2-12 GHz frequency region. The rotational spectra of two distinct nuclear spin isomers of syn-syn-carbonyl diisothiocyanate, ortho and para, were recorded and analyzed. Experimental molecular rotational parameters for the identified rotational and nuclear spin isomers were determined, including rotational constants, centrifugal distortion constants, and nuclear quadrupole coupling constants. The two nuclear spin isomers are distinguished by unique hyperfine splitting signatures in their rotational spectra as an outcome of their different nuclear spin states. The relative abundances of the two observed conformers in the gas phase were estimated from the intensity of their rotational transitions. Following detection of singly substituted rare isotopologues of the syn-syn conformer, a partial substitution (rs) structure was determined.

Rotational spectra of singly substituted rare isotopologues of two conformers of 3,3,3-trifluoropropanol

The conformational distribution and the associated conformational conversion paths of 3,3,3-trifluoropropanol (TFP) were explored experimentally and theoretically using jet-cooled chirped pulse and cavity Fourier transform microwave spectroscopy in tandem with quantum chemical calculations. Rotational spectra of two TFP conformers, as well as their singly substituted 13C, 18O, and OD isotopologues, were measured and analyzed. The semi-experimental equilibrium rotational constants of the two conformers were also extracted for all isotopologues using the anharmonic calculations and used to obtain the semi-experimental equilibrium geometries.

Implementation of rare isotopologues into machine learning of the chemical inventory of the solar-type protostellar source IRAS 16293-2422

Using machine learning methods to model and predict molecular column densities toward the Class 0 protostar IRAS 16293-2422B.

Computed spectroscopic properties of HCN, HNC, and all their D, 13C, and 15N substituted isotopologues

ABSTRACT Starting from ab initio electronic structure data, we develop parametrized analytic potential energy surfaces for the HCN and HNC isomers by variationally calculating rovibrational energy levels and adjusting the potential parameters so as to get agreement with experimentally derived transition frequencies to within about 1 cm−1. We also determine an analytic expression in terms of molecular parameters to effortlessly calculate the rovibrational energy levels. We use the obtained empirical potentials to calculate rovibrational levels for eight isotopologues of HCN and eight of HNC up to about 4000 cm−1 above the ground state. The energy levels are estimated to be accurate to within about 3 cm−1 based on comparison to experimental rovibrational transition frequencies for H12C14N, H12C14N, H13C14N, and H12C15N. For all 16 isotopologues, we calculate the zero-point energy and in nine cases we can compare with experimentally derived values. In these comparisons, the variationally obtained ZPE is within 5 cm−1 of the experimentally derived value, while the closed expression gives values within 6 cm−1 of the experimental values. For all 16 isotopologues, we also give molecular parameters from which the energy levels can easily be calculated using the closed expression. Endo- and exoergicities are given for 12 isotopic exchange reactions involving HCN/HNC and some isotopologues together with pre-exponential factors that should be useful in future modelling studies of rare isotopologues.

M 1–92 Revisited: New Findings and Open Questions: New NOEMA Observations of Minkowski’s Footprint

PN M 1–92, also known as Minkowski’s Footprint, is a textbook example of a massive pre-planetary nebula. It presents all the characteristics of this type of source: non-spherical symmetry (bipolar cylindrical symmetry in this case), high-velocity gas emission, large amounts of linear momentum and kinetic energy (momentum excess), and a self-similar growing structure. We have revisited this object by performing new NOEMA observations (with half arc-second resolution) of a wealth of molecules, including the rare isotopologues of CO, as well as other less abundant species. These maps provide new insights into the origin of this source. Our findings include the discovery of molecular species in the ionised regions of the nebula, confirming its shocked origin; the structure of the massive equatorial component, including the presence of active wind collisions; and the strong evidence that the AGB evolution of the source was terminated prematurely, probably due to the huge mass loss event that resulted in the formation/acceleration of the present nebula.

Gas properties in the Early Universe deciphered from spectral line surveys of high-z objects: The Cloverleaf Quasar

Molecular lines observed in remote quasars arise from exceptionnally strong starburst regions in the vicinity of the QSO. Their study offers a unique opportunity to probe the gas physical and chemical properties at the epoch of peak star formation (z=2-3). We report the preliminary results of an on-going mm/sub-mm spectral line survey of the Cloverleaf Quasar (z=2.6), the archetype of gravitationally lensed quasars. We identify 14 molecular species, including rare isotopologues of CO and HCO+. The high gas density tracers HCO+, HCN, HNC and CN are detected through several rotational transitions, up to J=8-7 (Eup/k ≃ 155 K). Their emission appears to arise from dense (> 106 cm−3) gas clumps embedded in a circumnuclear disk with a flat rotation curve.

ALCHEMI, an ALMA Comprehensive High-resolution Extragalactic Molecular Inventory

Context.The interstellar medium is the locus of physical processes affecting the evolution of galaxies which drive or are the result of star formation activity, supermassive black hole growth, and feedback. The resulting physical conditions determine the observable chemical abundances that can be explored through molecular emission observations at millimeter and submillimeter wavelengths.Aims.Our goal is to unveiling the molecular richness of the central region of the prototypical nearby starburst galaxy NGC 253 at an unprecedented combination of sensitivity, spatial resolution, and frequency coverage.Methods.We used the Atacama Large Millimeter/submillimeter Array (ALMA), covering a nearly contiguous 289 GHz frequency range between 84.2 and 373.2 GHz, to image the continuum and spectral line emission at 1.6″(∼28 pc) resolution down to a sensitivity of 30 − 50 mK. This article describes the ALMA Comprehensive High-resolution Extragalactic Molecular Inventory (ALCHEMI) large program. We focus on the analysis of the spectra extracted from the 15″ (∼255 pc) resolution ALMA Compact Array data.Results.We modeled the molecular emission assuming local thermodynamic equilibrium with 78 species being detected. Additionally, multiple hydrogen and helium recombination lines are identified. Spectral lines contribute 5 to 36% of the total emission in frequency bins of 50 GHz. We report the first extragalactic detections of C2H5OH, HOCN, HC3HO, and several rare isotopologues. Isotopic ratios of carbon, oxygen, sulfur, nitrogen, and silicon were measured with multiple species.Concluison.Infrared pumped vibrationaly excited HCN, HNC, and HC3N emission, originating in massive star formation locations, is clearly detected at low resolution, while we do not detect it for HCO+. We suggest high temperature conditions in these regions driving a seemingly “carbon-rich” chemistry which may also explain the observed high abundance of organic species close to those in Galactic hot cores. TheLvib/LIRratio was used as a proxy to estimate a 3% contribution from the proto super star cluster to the global infrared emission. Measured isotopic ratios with high dipole moment species agree with those within the central kiloparsec of the Galaxy, while those derived from13C/18O are a factor of five larger, confirming the existence of multiple interstellar medium components within NGC 253 with different degrees of nucleosynthesis enrichment. The ALCHEMI data set provides a unique template for studies of star-forming galaxies in the early Universe.

Simultaneous Calculation of Chemical and Isotope Equilibria Using the GEOCHEQ_Isotope Software: Oxygen Isotopes

—The GEOCHEQ_Isotope software package, elaborated previously for modeling chemical and carbon isotope equilibria in hydrothermal and hydrogeochemical systems by minimizing the Gibbs energy, is extended to the simultaneous calculation of carbon and oxygen isotopic effects. Similar to what was done for carbon, the β-factor formalism was used to develop algorithms and a database for calculating the isotopic effects of oxygen. According to the developed algorithm, the Gibbs energy of formation of a rare isotopologue, G*(P, T), is calculated through the Gibbs energy of formation of the main isotopologue, the value of the β18O factor of this substance, and the mass ratio of the rare (18O) and main (16O) isotopes. The isotope mixture is assumed to be ideal. The temperature dependence of the β-factor is unified as a polynomial in reciprocal absolute temperature. Necessary information on oxygen isotope equilibria involving important geochemical compounds was critically analyzed, and the available data were reconciled and modified. The temperature dependences of the β18O-factors were correspondingly optimized. The thermodynamic database was updated by adding information on the temperature dependence of β18O-factors specified by polynomial coefficients for each substance. The usage of the GEOCHEQ_Isotope software package and the corresponding database is demonstrated by modeling the dependence of oxygen and carbon isotope fractionation factors on the acidity of the solution (pH) in a carbonate hydrothermal system. The simulation results are in a good agreement with experimental data available from the literature. The enrichment of dissolved carbonates in the 18O heavy oxygen isotope relative to water decreases with increasing pH of the system. At the same time, a pH increase results in a decrease in the negative carbon isotope shift between calcite and dissolved carbonates. At high pH values (~11), the isotope shift inversion and the enrichment of the dissolved carbonate in the heavy carbon isotope relative to calcite are predicted.

Recognizing the pathways of microbial methanogenesis through methane isotopologues in the subsurface biosphere

Microbial methanogenesis is a significant component in the global carbon cycle, a driver of greenhouse warming from atmospheric methane, and contributes to natural gas resources. There are several metabolic pathways of methanogenesis, and it is challenging to discriminate between them and quantify their relative contributions in natural settings. Here we measure and compile four rare isotopologues of methane (13CH4, 12CH3D, 13CH3D and 12CH2D2) from the Qaidam Basin (China) and a large set of previous data across the world to identify distinctive fingerprints of two principal sources of subsurface microbial methane — hydrogenotrophic and methylotrophic methanogenesis — and use those fingerprints to deconvolve the budgets of microbial methane in the Qaidam Basin. Our data show that biogenic methanes in the Qaidam Basin have equilibrium Δ18/Δ13CH3D values respect to reservoir temperature without anaerobic methane oxidation. Our results suggest that methylotrophic methanogenesis produces methane with large deficits in 13CH3D and 12CH2D2 relative to that controlled by homogeneous equilibrium among methane isotopologues at ambient environmental temperatures, whereas hydrogenotrophic methanogenesis produces methane with 13CH3D abundance near equilibrium and relatively subtle 12CH2D2 deficits. We find a good linear correlation between the Δ13CH3D value of natural biogenic methane and independent estimates of the fraction of hydrogenotrophic (methylotrophic) methanogenesis, based on established interpretations of hydrogen isotope data. These findings are consistent with studies of laboratory cultures, which also show methylotrophic methane is more depleted in clumped isotopologues (13CH3D and 12CH2D2) than hydrogenotrophic methane, though both forms of cultured (hydrogenotrophic vs. methylotrophic) methane exhibit strong deficits in both isotopic species. The sensitivity of clumped isotopologues to methanogenesis pathways in natural settings provides a powerful tool for monitoring the activity of methanogenic microbial communities in the subsurface. Anomalies of both studied clumped isotopologues (Δ13CH3D and Δ12CH2D2) decrease over time in wells that have been re-sampled repeatedly, suggesting that such measurements are capable of detecting and quantifying shifts in proportions of these two metabolic pathways over the timescales of gas production history.

Rotational spectroscopy of imidazole: Accurate spectroscopic information for three vibrationally excited states and the heavy-atom isotopologues up to 295 GHz

We report our analysis of the pure rotational spectra of low-lying vibrationally excited states and heavy-atom rare isotopologues of imidazole. To facilitate searches for imidazole in the interstellar medium, we previously described the analysis of the rotational spectrum of the imidazole main isotopologue across the 2–295 GHz range, and we extend this analysis here. Structure optimisation and anharmonic frequency calculations were performed to aid the spectral analysis. Three vibrationally excited states of imidazole were assigned in our room-temperature spectra, with energies up to approximately 670 cm−1 above the vibronic ground state. The vibrational states could act as temperature probes in warmer star-forming regions. The 13C and 15N heavy-atom isotopologues were assigned, which allowed for the structure of imidazole in the gas phase to be determined. Structural comparisons are drawn between the related heterocyclic molecules hydantoin and imidazolidine. An experimental gas-phase structure of the former is also determined in this work. The potential detection of the isotopologues could help deduce formation pathways towards imidazole and other nitrogen-containing cyclic compounds in interstellar space.

Physical Conditions of Gas Components in Debris Disks of 49 Ceti and HD 21997

Abstract Characterization of the gas component in debris disks is of fundamental importance for understanding their origin. To address this goal, we have conducted non-LTE (local thermodynamic equilibrium) analyses of the rotational spectral lines of CO including those of rare isotopologues (13CO and C18O) that have been observed toward the gaseous debris disks of 49 Ceti and HD 21997 with the Atacama Large Millimeter/submillimeter Array (ALMA) and the Atacama Compact Array (ACA). The analyses have been carried out for a wide range of H2 density, and the observed line intensities are found to be reproduced as long as the H2 density is higher than 103 cm−3. The CO column density and the gas temperature are evaluated to be (1.8–5.9) × 1017 cm−2 and 8–11 K for 49 Ceti and (2.6–15) × 1017 cm−2 and 8–12 K for HD 21997, respectively, where the H2 collision is assumed for the rotational excitation of CO. The results do not change significantly even if electron collision is considered. Thus, CO molecules can be excited under environments containing no H2 or a small number of H2 molecules, even where collisions with CO, C, O, and C+ would make an important contribution to the CO excitation in addition to H2. Meanwhile, our result does not rule out the case of abundant H2 molecules. The low gas temperature observed in the debris disks is discussed in terms of inefficient heating by interstellar and stellar UV radiation.

Evidence for methane isotopic bond re-ordering in gas reservoirs sourcing cold seeps from the Sea of Marmara

The measurement of methane clumped isotopologues (Δ13CH3D and Δ12CH2D2) allows exploring isotope bond ordering within methane molecules, and may reveal equilibrium temperatures. Whether such temperature reflects the formation or re-equilibration temperature of the methane is not well understood, but would have critical implications for the use of methane clumped isotopologues as geo-thermometers. Here we investigate gas bubbles from vigorous emissions at cold seeps (n = 14) in the Sea of Marmara, Turkey. These cold seeps are sourced from deeper sedimentary reservoirs. Conventional geochemical tracers such as carbon and hydrogen bulk isotopic ratios (13C/12C and D/H) or n-alkane molecular ratios, suggest these gases reflect various degrees of mixing between thermogenic and microbial sources. Some samples would generally be considered purely microbial in origin (C1/C2+>1500; δ13C<−60‰). We report measurements of Δ13CH3D and Δ12CH2D2 showing that a fraction of those gases are in internal thermodynamic equilibrium, with the abundances of the two mass-18 isotopologues indicating concordant temperatures of ∼90°C and ∼130°C. These concordant temperatures are recorded by gases of putative microbial and thermogenic origin; the temperatures of equilibration are irrespective of the formation mechanism of the gases. We conclude that the two high-temperatures recorded by Δ13CH3D and Δ12CH2D2 are best explained by non-enzymatic re-equilibration at two local subsurface temperatures. First principles suggest that unequal rates of exchange are possible. Disequilibrium signatures where the two isotopologues yield discordant apparent temperatures are exhibited by other samples. In those cases the data define a trend of variable Δ13CH3D at nearly constant Δ12CH2D2. These signatures are enigmatic, and we investigate and reject multiple possible explanations including mixing, diffusion or Anaerobic Oxidation of Methane. Different rates of re-equilibration between the two rare isotopologues are implied, although lacks experimental foundation at present. In general, all of these data point towards re-equilibration of the mass-18 methane isotopologues as an important process.

Infrared Color Separation between Thin-shelled Oxygen-rich and Carbon-rich AGB Stars

Abstract We present 43 GHz VLA spectra for 51 AGB sources with the goal of verifying an infrared (IR) color cut intended to separate carbon-rich (C) and oxygen-rich (O) AGB sources throughout the Galaxy. The color cut is a simple line in the [K s ] − [A] versus [A] − [E] color–color diagram based on 2MASS and MSX photometry, and was originally derived from SiO detection rates in the Bulge Asymmetries and Dynamical Evolution (BAaDE) sample. The division is fully supported by the spectra presented here, which show that SiO maser detections lie on the O-rich side, and SiO nondetections and a single HC3N detection are found on the C-rich side of the division. We further compare the color cut with classifications of the sources based on Low-Resolution Spectra from the Infrared Astronomical Satellite, and find good agreement, verifying that the division is a reliable and efficient method for differentiating O- and C-rich AGB sources. These observations also demonstrate that single lines detected in the BAaDE survey around 42.9 GHz are almost certainly the 29SiO v = 0 line. SiO maser sources where this rare isotopologue transition is brighter than the dominant 28SiO lines have not been reported before, and our observations show that these sources can reverse their behavior such that the typical ratios of 28SiO and 29SiO are restored within a few years.

Rotational spectroscopy of rare iron monoxide isotopologues: A mass-independent analysis

We present pure rotational transitions of the rare iron monoxide isotopologues. , and in their lowest spin states . For , the rotational spectrum reveals hyperfine splitting due to the nuclear spin of . We use Dunham-like parameters to analyse the new laboratory data together with data from the literature. In particular, we are able to derive the Born–Oppenheimer breakdown parameters and and the corresponding equilibrium bond length of . With these new accurate molecular parameters line positions on a sub-MHz accuracy level can be calculated, including those of the radioactive isotopologue . The new data allow for an astronomical search for the rare isotopologues using sensitive radio telescopes, like the Atacama Large Millimetre/submillimetre Array.

フッ化型同位体分子計測：エタン、エタノールの13C-13C二重置換同位体分子計測法の開発

フッ化型同位体分子計測：エタン、エタノールの13C-13C二重置換同位体分子計測法の開発