Conformity and precision of CO2 densimetry in CO2 inclusions: microthermometry versus Raman microspectroscopic densimetry

To assess the ability of densimetry for CO₂ fluid in CO₂ inclusions, we compare two methods, microthermometry and Raman microspectroscopic densimetry for CO₂. The comparative experiment was performed for nine CO₂ inclusions in three mantle xenoliths. The results are as follows: (1) microthermometry precisely determines CO₂ density with the range of 0.65 to 1.18 g/cm³ compared with Raman microspectroscopic densimetry; (2) CO₂ density obtained by Raman microspectroscopic densimetry is fairly consistent with that by microthermometry; (3) it is hard to determine CO₂ density in CO₂ inclusion with diameter of less than around 3 µm using microthermometry; and (4) microthermometry can be applied only to the CO₂ inclusion whose CO₂ density ranges from around 0.65 to 1.18 g/cm³, whereas the Raman microspectroscopic densimetry is applicable to CO₂ density ranging from 0.1 to 1.24 g/cm³. The above features carry the potential for estimation of depth origin of mantle‐derived rocks. The depth where the rocks were trapped by host magma can be estimated using both geothermometric data and CO₂ fluid density in CO₂ inclusions in the rocks. Typical precisions of density of CO₂ in CO₂ inclusions obtained by the Raman microspectroscopic densimetry (~0.01 g/cm³) and by the microthermometry (< 0.001 g/cm³) correspond to uncertainties in the depth origin of 2.4 km and < 1.7 km, respectively, at 1000 ± 50 °C. In case of the mantle under 750–1250 °C and 1 GPa, the CO₂ fluid has a density ranging from 1.06 g/cm³ to 1.21 g/cm³, which are well measured by the Raman microspectroscopic densimetry. Combination of both densimetries for CO₂ in mantle minerals elucidates the deep structure of the Earth. Copyright © 2012 John Wiley & Sons, Ltd.     

CO2 laser saturation Stark spectra and global rovibrational analysis of the main isotopic species of carbonyl sulfide (OC34S,O13CS,and 18OCS)

Stark spectra of OC³⁴S, O¹³CS, and ¹⁸OCS have been recorded with an intracavity CO₂ laser spectrometer. The observed transitions are the 2ν₂ band and the associated hot bands from ν₂¹, ν₁, 2ν₂⁰, 2ν₂², ν₁ + ν₂¹, 3ν₂¹, and 3ν₂³. One line has also been observed in the 00⁰1 ← 02⁰0 band of OC³⁴S. For each isotopic species of OCS, a global weighted least-squares analysis has been applied simultaneously on all available zero-field and Stark data, yielding coherent sets of rovibrational and electrical molecular parameters. From the equilibrium rotational constants we have deduced an improved equilibrium structure for the OCS molecule.     

Absolute line intensities and self-broadening coefficients in the ν3 − ν1 band of carbon dioxide

Using a tunable diode-laser spectrometer, we have measured the self-broadening coefficients and strengths of 26 absorption lines in the ν₃ ? ν₁ band of ¹²CO₂ and ¹³CO₂ at room temperature. These lines, ranging from P(34) to R(40), are located around 960.9 and 913.4 cm^?1, respectively for the ¹²CO₂ and ¹³CO₂ molecules. The collisional widths and the intensities were obtained by fitting Voigt and Rautian and Sobel’man profiles to the measured shapes of the lines. From the individual line intensities and using a least-squares method, we have determined the vibrational band strength as well as the Herman–Wallis factors for the ν₃ ? ν₁ band of ¹²CO₂ and ¹³CO₂.     

Raman intensity measurements of the Fermi diad ν1, 2ν2 in CO2 and CO2

Intensity measurements of the ν₁, 2ν₂ vibrational Raman bands of ¹²CO₂ and ¹³CO₂ lend support to Amat's suggestion that the unperturbed 02⁰0 level is above the 10⁰0 level for ¹²CO₂. For ¹³CO₂, however, the ordering of the levels is reversed.     

High accurate peak positions for calibration purposes with the lowest fundamental bands ν2 of N2O and CO2

The lowest fundamental vibration rotation bands ν₂ of nitrous oxide (N₂O) and carbon dioxide (CO₂) have been measured with a Fourier transform spectrometer at the resolution of 0.001 cm⁻¹. The spectra have been calibrated with the high accurate peak positions of the carbonyl sulfide (OCS) ν₂ band, which has been recently produced as a candidate for a secondary standard by calibrating first the 2ν₂ band with the CO₂ laser bands around 10 μm and then transferring the calibration to ν₂ with the internal energy levels of OCS. In the present work the OCS ν₂ and ν₁ bands were measured together with the spectra of N₂O and CO₂. Then the OCS ν₁ band was measured by calibrating it with the 2ν₂ band of OCS. The linearity of the wavenumber scale was checked by comparing the corresponding line positions in the OCS ν₁ band in these two separate measurements. The absolute accuracy of the ν₂ band centers of N₂O and CO₂ were evaluated to be 6.8 × 10⁻⁶ and 8.4 × 10⁻⁶ cm⁻¹, respectively.     

Raman spectroscopic study of the magnesium carbonate mineral hydromagnesite (Mg5[(CO3)4(OH)2]· 4H2O)

Magnesium minerals are important for understanding the concept of geosequestration. One method of studying the hydrated hydroxy magnesium carbonate minerals is through vibrational spectroscopy. A combination of Raman and infrared spectroscopy has been used to study the mineral hydromagnesite. An intense band is observed at 1121 cm⁻¹, attributed to the CO₃²⁻ν₁ symmetric stretching mode. A series of infrared bands at 1387, 1413 and 1474 cm⁻¹ are assigned to the CO₃²⁻ν₃ antisymmetric stretching modes. The CO₃²⁻ν₃ antisymmetric stretching vibrations are extremely weak in the Raman spectrum and are observed at 1404, 1451, 1490 and 1520 cm⁻¹. A series of Raman bands at 708, 716, 728 and 758 cm⁻¹ are assigned to the CO₃²⁻ν₂ in‐plane bending mode. The Raman spectrum in the OH stretching region is characterized by bands at 3416, 3516 and 3447 cm⁻¹. In the infrared spectrum, a broad band is found at 2940 cm⁻¹, which is assigned to water stretching vibrations. Infrared bands at 3430, 3446, 3511, 2648 and 3685 cm⁻¹ are attributed to MgOH stretching modes. Copyright © 2011 John Wiley & Sons, Ltd.     

High-pressure measurements of CO2 absorption near 2.7 μm: Line mixing and finite duration collision effects

Room-temperature, high-pressure (1–30 atm) measurements of CO₂ absorption are carried out near 2.7 μm to study line mixing and finite duration collision effects on transitions in the ν₁+ν₃ and 2ν₂+ν₃ vibrational bands. Two distributed feedback diode lasers are used to measure CO₂ transitions near 3631–3635 cm^?1 and 3644–3646 cm^?1, and an FTIR spectrometer covers the entire ν₁+ν₃ and 2ν₂+ν₃ bands from 3500 to 3800 cm^?1. The experiments are carried out in CO₂–air and CO₂–Ar mixtures to observe the non-ideal effects under the influence of different perturbers. Measurements are compared with simulations using the Voigt line shape to analyze the deviation from the Lorentzian behavior with increasing gas density, and show significant deviation from this model at high gas densities. Line shape models using empirical corrections or dynamically based scaling laws are evaluated by comparison to the measured high-density spectra. Although none of the models is able to predict the measured spectra accurately, the line mixing model of Niro et al. [24] does an overall good job but overestimates the band centers by about 4–9%. In light of these observations, challenges of developing a CO₂ sensor for high-pressure combustion applications are discussed.     

Continuous measurements of stable carbon isotopes in CO2 with a near-IR laser absorption spectrometer

A near-IR laser absorption spectrometer using a technique of wavelength modulation spectroscopy is used to measure stable carbon isotope ratios of ambient CO₂ (δ¹³C) via the absorption lines ¹²CO₂ R(17) (2ν₁ + ν¹₂ − ν¹₂ + ν₃) at 4978.205 cm⁻¹ and ¹³CO₂ P(16) (ν₁ + 2ν₂ + ν₃) at 4978.023 cm⁻¹. The isotope ratios are measured with a reproducibility of 0.02‰ (1σ) in a 130-s integration time over a 12-h period. The humidity effect on δ¹³C values has been evaluated in laboratory experiments. The δ¹³C values of CO₂ in ambient air were measured continuously over 8 days and agreed well with those from isotope ratio mass spectrometry of canister samples. The spectrometer is thus capable of real-time, in situ measurements of stable carbon isotope ratios of CO₂ under ambient conditions.     

Assignment of submillimeter laser lines in methyl chloride

Assignments are proposed here for 19 far infrared laser lines in CH₃Cl excited by a CO₂ laser and for the CH₃Cl transitions which are pumped. In each case the chlorine isotopic species involved is determined. In addition, a complete set of band parameters is obtained for the ν₆ band of CH₃³⁷Cl as well as for CH₃³⁵Cl. The vibrational isotopic shift Δν(35–37) is found to be 0.386 cm^?1 for the ν₆ band of CH₃Cl.     

Laser Stark spectroscopy of methyl cyanide in the 10-μm region: Analysis of the ν4 and ν7 bands,and the ν7, 3ν81 interaction

About 550 Stark tuned resonances of the ν₄ and ν₇ vibration-rotation bands of CH₃CN were measured using ¹²CO₂, ¹³CO₂, and N₂O lasers. These data are combined with 26 microwave measurements and fitted to a model which includes l-type doubling in ν₇, ν₄-ν₇ Coriolis coupling, and ν₇-³ν₈¹ Coriolis and Fermi couplings. The infrared and microwave data can be reproduced with standard deviations of 7 MHz and 40 kHz, respectively. The many vibration-rotation parameters and the dipole moments are determined with great accuracy. A complete list of derived parameters is given in Table I.     

Laser Stark and laser microwave double resonance spectroscopy of fluoroacetylene with the CO2 laser

The CO₂ laser Stark spectrum of fluoroacetylene was identified for the ν₃, ν₃ + ν₄ ? ν₄, and ν₃ + ν₅ ? ν₅ vibrational bands. The origins of these bands were precisely determined (±0.0003 cm^?1) to be 1061.4452, 1059.0639, and 1064.6960 cm^?1. A CO₂ laser microwave double resonance experiment in the presence of the Stark field is described. This technique was applied to assignment of the Stark spectrum, calibration of the Stark electrode spacing, and precise determination (±0.0003 D) of dipole moment. The dipole moments of the HCCF molecule in the ground, ν₃, ν₄, ν₅, ν₃ + ν₄, and ν₃ + ν₅ vibrational states are 0.7207, 0.7447, 0.6557, 0.7441, 0.6769, and 0.7689 D.     

Raman and mid‐IR spectroscopic study of the magnesium carbonate minerals—brugnatellite and coalingite

Two hydrated hydroxy magnesium carbonate minerals brugnatellite and coalingite with a hydrotalcite‐like structure were studied by Raman spectroscopy. Intense bands are observed at 1094 cm⁻¹ for brugnatellite and at 1093 cm⁻¹ for coalingite attributed to the CO₃²⁻ν₁ symmetric stretching mode. Additional low intensity bands are observed at 1064 cm⁻¹. The existence of two symmetric stretching modes is accounted for in terms of different anion structural arrangements. Very low intensity bands at 1377 and 1451 cm⁻¹ are observed for brugnatellite, and the Raman spectrum of coalingite displays two bands at 1420 and 1465 cm⁻¹ attributed to the (CO₃)²⁻ν₃ antisymmetric stretching modes. Very low intensity bands at 792 cm⁻¹ for brugnatellite and 797 cm⁻¹ for coalingite are assigned to the CO₃²⁻ out‐of‐plane bend (ν₂). X‐ray diffraction studies by other researchers have shown that these minerals are disordered. This is reflected in the difficulty of obtaining Raman spectra of reasonable quality and explains why the Raman spectra of these minerals have not been previously or sufficiently described. A comparison is made with the Raman spectra of other hydrated magnesium carbonate minerals. Copyright © 2008 John Wiley & Sons, Ltd.     

Study of the ν2 + ν3 and 2ν6 infrared bands of CH379Br and CH381Br

The rotational analysis of the ν₂ + ν₃ band, centered around 1912 cm^?1, and of both components 2ν₆^±2 and 2ν₆⁰, centered about 1912 and 1904 cm^?1, respectively, has been carried out from a Fourier transform spectrum having a resolution limit of 0.005 cm^?1. A standard deviation of about 0.001 cm^?1 was obtained for about 750 lines of the unperturbed 2ν₆^±2 component for both isotopic species. The ν₂ + ν₃ band, stronger than 2ν₆^±2, is perturbed by two resonances: a Coriolis resonance with the very weak ν₃ + ν₅ band, no line of which has been observed, and an anharmonic resonance with 2ν₆⁰, only four K subbands of which have been observed. For both isotopic species, a standard deviation of about 0.002 cm^?1 has been obtained for about 750 lines of ν₂ + ν₃ and 2ν₆⁰.     

Transferring the high accuracy of the 10 μm CO2 laser bands to far infrared region with internal calibration of CS2

The main aim of the work is to transfer the high accuracy of the CO₂ laser bands around 10 μm to far infrared regions around 400 and 250 cm⁻¹ for secondary standards. The bands ν₁ + ν₂ and 3ν₂ of CS₂ were measured on the Bruker IFS 120 HR Fourier spectrometer in Oulu with special care and calibrated against CO₂. In the second stage the ν₂ region around 400 cm⁻¹ was measured at a resolution of 0.001 cm⁻¹. This spectrum was calibrated against 3ν₂ internally with the CS₂ band system using ladders formed with rotational lines in the bands ν₂, 2ν₂ − ν₂ and 3ν₂ − 2ν₂. Further, the difference band ν₁ − ν₂ at 263 cm⁻¹ together with accompanying hot bands was measured on a similar spectrometer in Lund, Sweden, but with a synchrotron radiation source. Using corresponding chains of lines as above this region was calibrated with ν₁ + ν₂. In this way, problems with conventional calibration could be avoided. Without the effect of the pressure shifts the absolute accuracy of 2.0 × 10⁻⁶ and 8.4 × 10⁻⁶ cm⁻¹ has been achieved at 400 and 250 cm⁻¹, respectively. Simultaneously the same calibration accuracy is also transferred to residual water lines around the CS₂ far infrared bands and the best H₂O lines will be given with literature comparisons. In addition to the calibration new results from the observed hot bands of CS₂ in the region of the bands ν₁ + ν₂ and 3ν₂ will be given.     

Discovery of multiple bands of isotopic CO2 in the prime spectral regions used when searching for CH4 and HDO on Mars

We present new measurements of vibrational band systems of isotopic carbon dioxide (CO₂) with multiple strong lines in the wavelength region 3.3-3.7 μm. In our ground-based searches for methane (CH₄) and other biomarker gases on Mars, we discovered two new vibrational band systems that we identify as the previously unknown ν₂+ν₃ band of ¹⁶O¹²C¹⁸O and the 2ν₁ band of the rare isotope ¹⁶O¹³C¹⁸O. We also extended and provide refined spectroscopic constants for the 2ν₁ band of ¹⁶O¹²C¹⁷O, detecting 38 new lines. The newly discovered 2ν₁ band of ¹⁶O¹³C¹⁸O at 3.7 μm and the 2ν₁ band of ¹⁶O¹²C¹⁷O at 3.6 μm extend over the prime spectral region used when searching for deuterated water (HDO) and formaldehyde (H₂CO) on Mars. The ν₂+ν₃ band of ¹⁶O¹²C¹⁸O at 3.3 μm interferes with the ν₃ band of CH₄ at 3.3 μm. If unrecognized, even weak bands of CO₂ can obscure searches for trace gases on Mars, so it is important to quantify them. Here, we report molecular parameters from the measured line positions that agree well with values calculated from the known energy levels of these isotopologues, and we provide absolute band strengths for each system.     

Vibration-rotation bands of CO2 and OCS in the region 540–890 cm−1

The regions of the ν₂ band of CO₂ and the ν₁ band of OCS have been simultaneously measured by the Fourier transform spectrometer (1, 2). The resolution achieved was now about 0.0045 cm^?1. A total of eight “hot” bands of ¹²C¹⁶O₂ and ¹⁶O¹²C³²S and the fundamental bands ν₂ of ¹³C¹⁶O₂ and ν₁ of ¹⁶O¹²C³⁴S have been reported.     

High-resolution spectroscopy of the 16-μm bending fundamental of CF4

The 16-μm bending fundamentals (ν₄) of ¹²CF₄, ¹³CF₄, and ¹⁴CF₄ have been observed at Doppler-limited resolution using a tunable PbSnSe semiconductor diode laser. The tetrahedral splittings of the rotational manifolds have been observed in all three branches, and in particular the dense and partially overlapping transitions in the Q branches have been resolved and assigned. A least-squares fit of the Hamiltonian, including off-diagonal terms, yielded five scalar and three tensor spectroscopic constants for each of the three isotopes. From these constants the upper-state rotational constant B₄ and the Coriolis constant ζ₄ have been calculated, together with some of the other molecular constants. An absorption feature at about 0.18 cm^?1 to the red of the main Q branch of each isotopic species has been identified as the Q branch of (ν₂ + ν₄) ? ν₂, which is the transition that lases when CF₄ is pumped by a CO₂ laser at 9.4 μm (i.e., in ν₂ + ν₄).     

Autoassociation du cyclohexanol. II - caracteristiques spectroscopiques des vibrateurs ν(OH) dans les complexes d'autoassociation.

From a thermodynamic model of associated solution, the molar extinction coefficients for the spectroscopically discernable ν(OH) vibrations of associated species of cyclohexanol in isooctane solutions at 25°C and 45°C are obtained. It is found that the molar extinction coefficients for the end hydroxyl group of open species and for the monomer band are very near (57 M^?1 cm^?1 at 25°C). For the hydrogen bonded hydroxyl groups, molar extinction coefficients at 25°C are found to be, in M^?1 cm^?1 units : 93 for the open dimer ($\text{ν}$ = 3515 cm^?1), 90 for the open trimer ($\text{ν}$ = 3440 cm^?1), 126 for the other i-mers ($\text{ν}$ = 3340 cm^?1).     

Laser Stark spectroscopy of the coriolis coupled ν2 and ν5 bands of CD3Cl

About 940 Stark resonances for CD₃³⁵Cl and 610 resonances for CD₃³⁷Cl have been measured by using a CO₂ laser with the 9- and 10-μm regions. They were assigned to 59 rovibrational transitions of ν₂ (J′ ≤ 37, K ≤ 14) and 200 of ν₅ (J′ ≤ 47, ?14 ≤ k′l′ ≤ +10) for ³⁵Cl, and 31 of ν₂ (J′ ≤ 12, K ≤ 10) and 175 of ν₅ (J′ ≤ 46, ?14 ≤ k′l′ ≤ +9) for ³⁷Cl. These data, combined with the microwave and FIR data in the ν₂ and ν₅ states, were analyzed by taking account of the Coriolis interaction between ν₂ and ν₅, and the (2, 2) and (2, ?1) interactions in ν₅. Several ΔK = +2 transitions of the ν₅ band were observed in the Stark spectra, and the ground state constants, A₀ and D_K0, were determined precisely for both ³⁵Cl and ³⁷Cl species. Also, the vibrationally induced dipole moments were obtained. The molecular constants and the zero-field transition frequencies of the ν₂ and ν₅ bands were determined.     

Raman spectroscopic study of the magnesium‐carbonate minerals—artinite and dypingite

Magnesium minerals are important in the understanding of the concept of geosequestration. The two hydrated hydroxy magnesium‐carbonate minerals artinite and dypingite were studied by Raman spectroscopy. Intense bands are observed at 1092 cm⁻¹ for artinite and at 1120 cm⁻¹ for dypingite, attributed ν₁ symmetric stretching mode of CO₃²⁻. The ν₃ antisymmetric stretching vibrations of CO₃²⁻ are extremely weak and are observed at 1412 and 1465 cm⁻¹ for artinite and at 1366, 1447 and 1524 cm⁻¹ for dypingite. Very weak Raman bands at 790 cm⁻¹ for artinite and 800 cm⁻¹ for dypingite are assigned to the CO₃²⁻ν₂ out‐of‐plane bend. The Raman band at 700 cm⁻¹ of artinite and at 725 and 760 cm⁻¹ of dypingite are ascribed to CO₃²⁻ν₂ in‐plane bending mode. The Raman spectrum of artinite in the OH stretching region is characterised by two sets of bands: (1) an intense band at 3593 cm⁻¹ assigned to the MgOH stretching vibrations and (2) the broad profile of overlapping bands at 3030 and 3229 cm⁻¹ attributed to water stretching vibrations. X‐ray diffraction studies show that the minerals are disordered. This is reflected in the difficulty of obtaining Raman spectra of reasonable quality, and explains why the Raman spectra of these minerals have not been previously or sufficiently described. Copyright © 2008 John Wiley & Sons, Ltd.