Ν3 Band Research Articles

Non-destructive Analytical Study of Raman Spectra Variations and Mechanisms of Calcite and Aragonite in Modern and Fossilized Oysters.

Oyster fossils are some of the most common bivalve mollusk fossils found all over the world, they are different from other fossils because the oyster is still alive in the present day, and the body structure of modern oyster is almost the same as that of ancient one. Therefore, we designed a control experiment comparing the Raman spectra of minerals from both modern oysters and fossil oysters to explore the mechanism of oyster's fossilization process, which is considered to be helpful for investigating biological evolution or paleoenvironment. The oyster fossil sample was found in Nagi-Cho, Okayama Prefecture, Japan. We focused on the variations of band position and full width half-maximum of ν1 Raman band (symmetric stretching mode) of calcite (CaCO3) from modern and fossil oysters and the mineral conversion between calcite and aragonite (CaCO3) around the adductor muscle inside the oyster. Compared to modern oysters, the ν1 band at around 1086 cm-1 of calcite from oyster fossils shifted to a high wavenumber region, and the possible reason for this phenomenon is considered an elemental substitution between Ca2+ and Mg2+. As for aragonite around adductor muscle in fossil oysters, it has been found by Raman spectra that most of the aragonite has been converted into calcite because calcite has a relatively more stable structure.

Helium Detection in Natural Gas Using Raman Spectroscopy.

Raman spectroscopy has great potential for quantitative analysis of natural gas. Helium is one of the components of natural gas and has a wide range of applications. It was believed that noble gases could not be detected using this technique due to the absence of their vibrational spectra. In this study, we demonstrated an approach to extracting the content of helium from the Raman spectrum of methane and carried out test measurements for the first time. The approach is based on the determination of changes in the ν1 band of methane caused by the influence of helium and other components. The necessary spectroscopic parameters characterizing the effect of methane (CH4), helium (He), nitrogen (N2), carbon dioxide (CO2), and ethane (C2H6) on the ν1 band of methane at a resolution of 0.35 cm-1 were obtained. The validation of the approach showed that the helium content in natural gas can be measured with an uncertainty of 1 mol% at a sample pressure of 50 bar. The measurement precision can be increased to 0.01 mol% by using a high-resolution spectrometer. The described method does not claim to replace helium detectors, but it can be considered a valuable addition to Raman gas analysis of natural gas in developing an all-in-one device. The possibilities for further improvement of the approach are also discussed.

High resolution analysis of the CD[formula omitted] deuterated methane: Extended investigation of the pentad region

A highly accurate rotational–vibrational analysis of Fourier transform infrared spectra of the 12CD4 molecule is presented. The high resolution infrared spectra were measured with a IFS125 HR Fourier transform interferometer from Bruker at an optical resolution of 0.003 cm−1 and analyzed in the 1750–2400 cm−1 region. Here the 2ν2, ν2+ν4, 2ν4, ν1 and ν3 bands (altogether, nine sub-bands of different symmetry) of the pentad are located. The number of 1213/1993/1576/77/1582 transitions with the Jmax = 23/23/23/14/32 were assigned to the 2ν2, ν2+ν4, 2ν4, ν1 and ν3 bands of 12CD4. The obtained experimental data were used for the determination of the upper ro-vibrational energy values. To provide more correct values of the upper energies, more than 7800 highly accurate “hot” transitions from the dyad region were additionally processed. In general, 4088 upper ro-vibrational energies of the pentad (for comparison, 2525 upper ro-vibrational energies with the value of Jmax=20 are known in the modern literature up to now) were determined, which were used then in the weighted fit procedure with a goal to determine the spectroscopic parameters (band centers, rotational, centrifugal distortion, tetrahedral splitting and resonance interaction parameters) of the effective Hamiltonian. The obtained drms value is 5.5×10−4 cm−1 which is almost one hundred times better than the reproduction of the same set of experimental data by the parameters known in the earlier literature.

Measurement and assignment of J = 5 to 9 rotational energy levels in the 9070-9370cm-1 range of methane using optical frequency comb double-resonance spectroscopy.

We use optical-optical double-resonance spectroscopy with a continuous wave (CW) pump and a cavity-enhanced frequency comb probe to measure the energy levels of methane in the upper part of the triacontad polyad (P6) with higher rotational quantum numbers than previously assigned. A high-power CW optical parametric oscillator, tunable around 3000 cm-1, is consecutively locked to the P(7, A2), Q(7, A2), R(7, A2), and Q(6, F2) transitions in the ν3 band, and a comb covering the 5800-6100cm-1 range probes sub-Doppler ladder-type transitions from the pumped levels with J' = 6 to 8, respectively. We report 118 probe transitions in the 3ν3 ← ν3 spectral range with uncertainties down to 300kHz (1 × 10-5cm-1), reaching 84 unique final states in the 9070-9370cm-1 range with rotational quantum numbers J between 5 and 9. We assign these states using combination differences and by comparison with theoretical predictions from a new abinitio-based effective Hamiltonian and dipole moment operator. This is the first line-by-line experimental verification of theoretical predictions for these hot-band transitions, and we find a better agreement of transition wavenumbers with the new calculations compared to the TheoReTS/HITEMP and ExoMol databases. We also compare the relative intensities and find an overall good agreement with all three sets of predictions. Finally, we report the wavenumbers of 27 transitions in the 2ν3 spectral range, observed as V-type transitions from the ground state, and compare them to the new Hamiltonian, HITRAN2020, ExoMol, and the WKMLC line lists.

Cavity ring-down spectroscopy of 14N216O near 0.83 µm

The cavity ring-down spectra (CRDS) of nitrous oxide were recorded at a pressure of 10 hPa in the 11,937–12,223 cm-1 range with a threshold sensitivity to absorption coefficient of the order of 6.5 × 10–11 cm-1. Three bands (ν1+5ν3, 6ν1+2ν3, and 3ν1+4ν3) were detected. The line centers and intensities were recovered from the observed spectra. The spectroscopic constants of the upper vibrational states and the vibrational transition dipole moment parameters were fitted to the measured line positions and intensities, respectively. It was found that the 3ν1+4ν3 band is in the interpolyad Coriolis resonance interaction with the 7ν1+7ν21 band. This interaction leads to the appearance in the spectra of the four extra lines of the 7ν1+7ν21 band.

First widespread occurrence of rare phosphate chladniite in a meteorite, winonaite Graves Nunataks (GRA) 12510: Implications for phosphide–phosphate redox buffered genesis in meteorites

Abstract The first widespread occurrence of rare Na-, Ca-, and Mg, Mn, Fe-bearing phosphate chladniite was observed in meteorite Graves Nunataks (GRA) 12510, which is a primitive achondrite that sits within the winonaite class. Numerous 1–500 µm chladniite grains were found, often on the margins between silicate clasts and the kamacite portions of the large metal veins that permeated through the sample. The largest chladniite grains are associated with merrillite, kamacite, taenite, troilite, albite, forsterite, diopside, and enstatite, with a few tiny chladniite grains and an apatite grain enclosed within merrillite. GRA 12510s average chladniite composition is Na2.7Ca1.25(Mg10.02Mn0.69Fe0.20)Σ10.91(PO4)9. Electron backscattered diffraction (EBSD) patterns indicate varying degrees of nucleation and growth of chladniite grains. Additionally, the first pure Raman spectrum of chladniite is described here, revealing primary ν1 bands at 954, 974, and especially 984 cm–1. The co-occurrence and close association of merrillite, apatite, chladniite, and P-bearing metallic phases within GRA 12510 suggests that the fO2 of IW-2 to IW-4 is an intrinsic property of the precursor chondritic material, and the phosphate-phosphide reaction may have buffered the final winonaite and IAB iron meteorite phase assemblages. Altogether, chladniite appears to form alongside other phosphates, with their chemistries reflecting the diverse environment of their formation. Meteoritic chladniite likely formed through subsolidus oxidation of schreibersite, scavenging Na from albite, Ca from diopside, Mg from enstatite/forsterite, Fe from kamacite/taenite, and Mn from alabandite/chromite when available. A P0-P5+ redox-buffered environment also has implications for thermometry and fast cooling rates, although more experiments are needed to extrapolate powder reaction rates to those of larger crystals. Furthermore, phosphide-phosphate buffered experiments may aid in investigating equilibrium chemistry at fO2 values between IW-2 and IW-4, which have been challenging to explore experimentally due to the limited availability of solid metal-metal oxide buffers between IW (Fe-FeO) and IW-5 (Cr-Cr2O3) at temperatures and pressures relevant to planetary interiors. Future investigations of phosphide-phosphate redox-buffered genesis at fO2 values between IW-2 and IW-4 have important implications for primitive meteorite constituents (e.g., CAI values), partially differentiated planetesimals and planets, including Mercury and core formation on Earth.

The ethylene absorption spectrum between 6075 and 8050 cm-1: Empirical line list and rovibrational assignments

The highly congested absorption spectrum of ethylene (C2H4) is analyzed between 6075 and 8050 cm-1. In the 6200–8050 cm-1 range, a list of about 32,650 lines is retrieved from a room temperature spectrum recorded by Fourier transform spectroscopy (P = 15.72 mbar, L = 45 m). This dataset was merged with a set of about 3460 lines available in the literature in the region of the strong ν5+ν9 band near 6150 cm-1. In addition, two FTS spectra at 130 K provide complementary information in the 6020–6320 cm-1 range (about 7570 lines).Relying on the position and intensity agreements with a line list of 12C2H4 transitions calculated by the variational method, a total of 4090 transitions is assigned to eighteen bands, ten of them being newly reported. All the reported assignments are confirmed by Lower State Combination Difference (LSCD) relations i.e. all the upper states (1749 in total) have coinciding determinations of their energies through several transitions (up to 6). The obtained empirical energy values are given and compared to their variational counterpart. As an additional validation test of the lower state assignments, the room temperature intensities are extrapolated at 130 K and compared to their experimental values. Overall, a large fraction of the strong lines of the region is assigned and the total intensity of the assigned transitions represents 46 and 55% of the total variational and experimental intensities at 296 K, respectively. In the considered range, variational positions deviate from measurements by a few cm-1 and the total variational absorption is underestimated by 40 %.

Mid-infrared high-resolution dual-comb spectroscopy: Intensity, broadening, and beyond-Voigt parameters of [formula omitted] and [formula omitted] lines

Using a high-resolution mid-infrared dual-comb spectrometer operating in the 1300 cm−1 spectral region, spectra of acetylene were recorded at room temperature. Spectroscopic parameters were measured in 3 vibrational bands of both 12C2H2 and 13C12CH2. Absolute line intensities (S0) and self-broadening coefficients (γ0self) were determined in the ν4+ν5, 2ν42+ν5−1⟵ν41 and ν41+2ν50⟵ν51 bands. For the main isotopologue, the collisional narrowing coefficients (ν0VC) as well as the speed-dependence of the broadening (γ2) and shifting (δ2) coefficients were measured in the ν4+ν5 band of the main isotopologue of acetylene. Theoretical line-shape models were fitted on experimental profiles using a homemade multi-spectrum fitting procedure to determine spectroscopic parameters. Excellent agreement with the literature was found for self-broadening coefficients and absolute line intensities in the ν4+ν5 band of 12C2H2. For the hot bands, good agreement with the literature is found within experimental uncertainties, while γ0self of those hot bands are also reported for the first time. Similarly, the rotational dependence of ν0VC is found to be close to previous works. γ2 and δ2 of 12C2H2, as well as S0 and γ0self of 13C12CH2 are also reported for the first time in this band.

Revisiting the IR Spectra of H2S in an Argon Matrix: Identification of (H2S)n (n ≤ 4) Clusters via the Spectral Assignment of νS-H Transitions.

Small-molecular clusters of H2S up to tetramer have been experimentally identified in a cold and solid argon matrix by the spectral assignment of νS-H fundamental transitions for different H2S:argon mixing ratios. Normal-mode frequency calculations at the MP2-CP/aug-cc-pV(Q + d)Z level have been used to support the spectral assignments. In addition, modulations in relative populations of different clusters due to the annealing of the deposited matrix and the preheating of the H2S-argon gas mixture before deposition reinforced the spectral assignments. Variations in mixing ratio, annealing of the matrix, and preheating of the gas mixture have also been used, in a combined manner, to unambiguously identify the ν1 and ν3 bands of the H2S monomer, which has been a matter of dispute for a long period. The two bands have been identified at 2634.4 and 2648.0 cm-1, respectively, while three bands at 2581.5, 2568.4, and 2547.6 cm-1 have been assigned to H-bonded dimers, cyclic trimers, and cyclic tetramers, respectively. Multiple bands within 2550-2580 cm-1 have been assigned to caged tetramers. The cooperative strengthening of S-H···S H bonds in cyclic H2S clusters was evident from the linear increment in νS-H spectral shifts with cluster size.

The D/H ratio in Titan’s acetylene from high spectral resolution IRTF/TEXES observations

We report observations of deuterated acetylene (C2HD) at 19.3μm (519 cm−1) with the Texas Echelon Cross Echelle Spectrograph on the NASA Infrared Telescope Facility in July 2017. Six individual lines from the Q-branch of the ν4 band were clearly detected with a S/N ratio up to 10. Spectral intervals around 8.0μm (745 cm−1) and 13.4μm (1247 cm−1) containing acetylene (C2H2) and methane (CH4) lines respectively, were observed during the same run to constrain the disk-averaged C2H2 abundance profile and temperature profile. Cassini observations with the Composite Infrared Spectrometer (CIRS) were used to improve the flux calibration and help to constrain the atmospheric model. The measured D/H ratio in acetylene, derived from the C2HD/C2H2 abundance ratio, is (1.22−0.21+0.27)× 10−4, consistent with that in methane obtained in previous studies. Possible sources of fractionation at different steps of the acetylene photochemistry are investigated.

Real-time monitoring of CH4 and N2O emissions from livestock using mid-infrared external cavity quantum cascade laser absorption spectroscopy

The largest share of greenhouse gas (GHG) emissions related to livestock originates from methane (CH4) and nitrous oxide (N2O) which have a far higher influence on global warming, it is therefore necessary to accurately monitor CH4 and N2O emissions to provide theoretical and practical basis for further estimating and regulating GHG emissions from livestock and improving livestock production performance. For the purpose of sensing CH4 and N2O emissions during livestock living process in real time, an optical sensor based on continuous-wave (CW) external cavity quantum cascade laser (EC-QCL) operating at room temperature was developed. CH4 and N2O absorption lines, located around 8 μm, of the ν4 and ν1 fundamental vibrational bands, respectively, were chosen for direct absorption spectroscopy, which allows for sensitive, selective and simultaneous measurement of CH4 and N2O concentrations. Use of a Herriot multi-pass cell with an effective path-length of 100 m, 1σ (SNR = 1) limits of detection of 26.8 ppbv, 20.3 ppbv and 0.01 % for CH4, N2O and H2O vapor were achieved, respectively. Field measurement of CH4 and N2O emissions from horses has been carried out in a stable over two weeks at the Vernaelde farm in Couderkerque Branche city, France. Concentrations of CH4 and N2O up to 10 times and 1.5 times higher than their levels in the local ambient air (∼ 2.12 ppmv and ∼ 427 ppbv) were observed, respectively.

New line list for the ν4 bands of the trans (790.117 cm–1) and cis (851.943 cm–1) conformers of nitrous acid (HONO): Accurate positions and absolute intensities

The goal of this work was to update and significantly improve the line lists that have been generated recently for 11 µm bands of the trans- and cis- conformer forms of nitrous acid (HONO) [Armante R, Perrin A, Kwabia Tchana F, Manceron L. The ν4 bands at 11 μm: linelists for the trans- and cis- conformer forms of nitrous acid (HONO) in the 2019 version of the GEISA database. Molecular Physics 2021;120:e1951860]. That 2019 version of the 11 µm line list was generated using the spectroscopic parameters that were available, at that time, in the literature. During the present study, we used high-resolution Fourier transform spectra recorded at 11 µm to perform a large investigation of line positions and intensities for the ν4 bands of the trans- and cis-conformer of HONO. The resulting set of experimental ν4 (absolute) intensities and of 41 energy levels were used to determine, by least squares fit computations, improved position and intensity parameters for the ν4 bands of the trans- and cis-conformer of HONO. For trans-HONO, the ν4 band appeared not to be perturbed, while for cis-HONO a weak high order B-type Coriolis, coupling together the 41 and 61 energy levels was evidenced for the first time. This new list is of potential interest for the IASI-NG (Infrared Atmospheric Sounding Interferometer - New Generation) instrument which will be launched on board the METOP-SG satellite in 2025.

Effect of Cage Occupancies on Molecular Vibrations of Methane in Structure H Clathrate Hydrate: Ab Initio Molecular Dynamics Simulation.

The structure H (sH) of methane hydrate, which has a distinctive structure with large (LL) cages capable of encapsulating multiple methane molecules, has been suggested as a methane reservoir in large icy bodies such as Titan, making it important in planetary science. This high-pressure phase, which exists in the GPa range, lends itself to the study of methane states and dynamics using powerful experimental techniques such as IR and Raman spectroscopy. However, the interpretation of the vibrational spectra of methane in the sH structure has been challenging because of the spectral complexities. The signals attributed to the methane molecules in the LL cage, as well as those of the other two cage types, overlap in the spectra. In this study, we investigated the microscopic origins of the shape of the C-H stretching vibration spectrum of methane in the LL cage using ab initio molecular dynamics (AIMD) simulations. For a single methane molecule in the LL cage, the ν3 band of the C-H stretching mode was observed at a higher frequency typical of isolated molecules in vacuum due to the large size of the LL cage. As the number of methane molecules in the LL cage increased beyond one, a tendency to blue-shift with increasing methane occupancy was observed, consistent with a loose-cage-tight-cage model. By characterizing the time correlation function of methane stretching vibrations based on the solvation number of methane and water molecules proximal to methane within the LL cage, we showed that the complicated spectral line shape observed in cases of higher methane occupancy in the LL cage resulted from the wider variation of the solvation shell states. Analysis of the solvation structures of the AIMD trajectories provided interpretations of the experimental spectral line shape, demonstrating the complementary nature of AIMD to the experiment and its effectiveness in analysis.

Coefficients of Carbon Dioxide Pressure-Induced Line Shift of Sulfur Dioxide at Room Temperature: The ν1 + ν3 Band

Coefficients of Carbon Dioxide Pressure-Induced Line Shift of Sulfur Dioxide at Room Temperature: The ν1 + ν3 Band

Collision-Induced Transformation of the Complex Vibrational Susceptibility of a Linear Molecule Using the Example of the ν3 Band of Carbon Dioxide

Collision-Induced Transformation of the Complex Vibrational Susceptibility of a Linear Molecule Using the Example of the ν3 Band of Carbon Dioxide

Analysis of the rotationally-resolved 3.3 µm region of C2H4 in natural isotopic abundance

Ethylene (or ethene) is a natural gas compound present in our atmosphere but also in the atmospheres of outer solar system planets such as Jupiter, Saturn, Uranus, Neptune and Saturn's moon Titan. However, a better knowledge of spectroscopic parameters is needed for this molecule in order to detect its presence and/or to derive its accurate concentration. We present here a detailed analysis and modeling of the strongly absorbing ν9 and ν11 fundamental bands in the 3.3 µm region. Due to the complexity of the observed spectrum, we have built a polyad scheme taking into account some fundamental bands previously analyzed thanks to the tensorial formalism developed in Dijon for asymmetric-top molecules. A four polyad system has been settled and the last P3 polyad contains four vibrational states: ν9, ν11, ν2+ν12 and 2ν10+ν12. A first frequency analysis has been performed, leading to 3328 assignments with a root mean square of 5.927 × 10−3 cm−1 and a standard deviation of 1.965 using 88 adjusted parameters, and we have also adjusted line intensities of 2190 lines by adjusting 14 parameters with an overall Root-Mean-Square (RMS) deviation of about 3.77 %. A new linelist of calculated lines in the 2900−3300 cm−1 region has been added to the ECaSDa and we plan to integrate it to the HITRAN database.

13CH4/12CH4 sensing using Raman spectroscopy

The paper presents a technique for measuring the concentration of 13CH4 in natural methane using Raman spectroscopy. The peak positions and the relative scattering cross-sections of the Q-branches for the most intense vibrational bands of 13CH4 are determined. Features of the 13CH4/12CH4 ratio measurement methods using Q-branches of the ν1 and ν3 bands were considered. It was shown that the 13CH4/12CH4 ratio can be determined by simulation of the ν3 bands of these molecules without the use of experimental spectra. In our experiments the measurement error of δ13C value was 10 ‰ using the 100-s exposure spectrum at a gas pressure close to 1 atm recorded on the developed Raman spectrometer. In addition, the Raman spectra of alkanes (up to n-hexane) in the range of 2850–3050 cm−1 at a resolution of 0.4 cm−1 are presented, and their integrated intensities in the ranges of the characteristic bands of 13CH4 and 12CH4 are provided. The data obtained make it possible to expand the capabilities of Raman gas analyzers in the mud gas logging industry.

Analysis of New Measurements of 18O-substituted Isotopic Species 16O16O18O and 16O18O16O of Ozone in the THz and Far-Infrared Ranges

High-resolution spectra corresponding to the rotational and the ν2–ν2 bands of the two most abundant isotopic species of ozone with one heavy 18O oxygen atom were recorded using SOLEIL synchrotron radiation source in the range 30–200 cm−1. Additionally, the ν2 vibrational-rotational bands were recorded between 550 and 880 cm−1 using a classical glowbar source that made it possible to extend and refine information compared to published data on the observed transitions of these bands. The analyses of recorded spectra permitted us to deduce experimental set of energy levels for the ground (000) and the first bending (010) vibrational states, which significantly exceeds literature data in terms of rotational quantum numbers. For both isotopic species, the weighted fits of all experimental line positions were carried out including previously published microwave data. As a result of this work, the improved values of rotational and centrifugal distortion parameters for the states (000) and (010) were obtained that permitted modelling the experimental line positions with a weighted standard deviation of 1.284 (2235 transitions) and 0.908 (4597 transitions), respectively, for 16O16O18O, and 1.168 (824 transitions) and 1.724 (2381 transitions) for 16O18O16O.

Branch dependence of halfwidths: Theoretical analysis of N2-broadened halfwidths of CH3Br in the v6 band

The N2-broadened halfwidths of CH3Br in the ν6 band have been calculated, along with the relaxation matrices W. These calculations employ our modified and refined versions of the Robert-Bonamy formalism. Extensive comparisons between the predicted halfwidths from the models and experimental measurements at T = 296 K are presented. Our latest model very closely matches the measurements. Meanwhile, we considered line mixing effects in the spectral profile of the RQ(j,0) sub-branch. Our method probably yields too large values of the off-diagonal elements of W. Finally, by comparing our calculated halfwidths with the data in HITRAN, we have observed generally good agreement, especially for lines with high values of j. However, the agreement becomes poor for lines with low values of j, deteriorating as j decreases. We identified a factor contributing to this poor agreement: the neglect of branch dependence in the development of HITRAN data. We believe that for lines with low values of j, this oversight undermines the reliability of the halfwidth values of CH3Br in HITRAN.

High-resolution ro-vibrational spectrum of H[formula omitted]S in highly excited vibrational states: Re-visiting the first decade

High resolution spectra of the H232S hydrogen sulfide are re-analyzed in the region of its first decade. Thanks to the improvement of the experimental conditions (in particular, an increase in both the instrumental resolution and the effective absorption path length by 1.5 times), on the one hand, and of the use of a more correct Hamiltonian model (which additionally takes into account the interactions of the bands under study with the ν1+4ν2 and 4ν2+ν3 bands), on the other hand, the information obtained as a result of the analysis of experimental data has been significantly expanded and improved compared to the previous status. In particular, (1) the total number of assigned lines has been increased by approximately 15 percent, (2) the maximum values of quantum numbers Jmax and Kamax for the assigned lines have been increased for the studied bands in average by 20–25 percent, (3) the number of obtained ”experimental“ energy levels of the upper vibrational states (especially for the (121) and (022) vibrational states) has been significantly increased, (4) despite the increase in the number of initial vibrational–rotational energies and quantum numbers Jmax and Kamax, the value of the standard deviation drms has improved 2.7 times for the obtained upper vibrational–rotational energies.