Line strengths of CO2: 4550-7000 cm

Line positions and strengths of ¹²C¹⁶O₂ were measured between 4550 and 7000 cm⁻¹ using near infrared absorption spectra recorded at 0.01-0.013 cm⁻¹ resolution with the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory at Kitt Peak, Arizona. These were retrieved from 42 laboratory spectra obtained at room temperature with five absorption cells having various optical path lengths (from 0.1 to 409 m) filled with natural and enriched samples of CO₂ at pressures ranging from 2 to 581 Torr. In all, band strengths and Herman-Wallis-like F-factor coefficients were determined for 58 vibration-rotation bands from the least-squares fits of over 2100 unblended line strengths; strengths of 34 of these bands had not been previously reported. Band strengths in natural abundance generally ranged from 3.30 × 10⁻²⁰ to 2.8 × 10⁻²⁵ cm⁻¹/molecule cm⁻² at 296 K. It was found that the high J transitions (J′ ? 61) of the 20012 ← 00001 band centered at 4977.8347 cm⁻¹ are perturbed, affecting both measured positions and strengths. Two other interacting bands, 21113e ← 01101e and 40002e ← 01101e, were also analyzed using degenerate perturbation theory. Comparisons with corresponding values from the literature indicate that absolute accuracies better than 1% and precisions of 0.5% were achieved for the strongest bands.     

O2A-band line parameters to support atmospheric remote sensing

Numerous satellite and ground-based remote sensing measurements rely on the ability to calculate O₂A-band [b¹Σ_g⁺←X³Σ_g⁻(0,0)] spectra from line parameters, with combined relative uncertainties below 0.5% required for the most demanding applications. In this work, we combine new ¹⁶O₂A-band R-branch measurements with our previous P-branch observations, both of which are based upon frequency-stabilized cavity ring-down spectroscopy. The combined set of data spans angular momentum quantum number, J′ up to 46. For these measurements, we quantify a J-dependent quadratic deviation from a standard model of the rotational distribution of the line intensities. We provide calculated transition wave numbers, and intensities for J′ up to 60. The calculated line intensities are derived from a weighted fit of the generalized model to an ensemble of data and agree with our measured values to within 0.1% on average, with a relative standard deviation of ≈0.3%. We identify an error in the calculated frequency dependence of the O₂A-band line intensities in existing spectroscopic databases. Other reported lineshape parameters include a revised set of ground-state energies, self- and air-pressure-broadening coefficients and self- and air-Dicke-narrowing coefficients. We also report a band-integrated intensity at 296 K of 2.231(7)×10⁻²² cm molec⁻¹ and Einstein-A coefficient of 0.0869(3) s⁻¹.     

Pressure dependence of spectral positions and widths of emission lines related to DJ→FJ electronic transitions in Sm ions doped into SrFCl single crystal

The pressure dependence of the peak positions and widths of the fluorescence lines corresponding to the ⁵D_J→⁷F_J electronic transitions in Sm²⁺-doped SrFCl crystals was measured at room temperature (RT) with a diamond anvil cell (DAC) and a high-pressure gas system, using silicone oil and gaseous helium as the pressure-transmitting medium, respectively. At RT and ambient pressure the electronic transitions ⁵D₀→⁷F_J (J= 0, 1, 2, 3) and ⁵D₁→⁷F_J (J=0, 1, 2) in Sm²⁺ ions yielded rather sharp spectral lines peaked at 14490, 14206, 13685, 13012 cm⁻¹ and 15823, 15533, 15012 cm⁻¹, respectively. At pressures up to 45 kbar in the DAC all these peaks shifted linearly to lower energies at the rates −2.36, −2.10, −2.43, −2.22 cm⁻¹/kbar and −2.35, −2.33, −2.47 cm⁻¹/kbar. Under purely hydrostatic gas pressure up to 7 kbar at RT the initial (normal pressure) widths of the ⁵D₀→⁷F₀, ⁵D₀→⁷F₁ and ⁵D₁→⁷F₀ lines having a Lorentzian profile (with corrected FWHM values of 1.55, 5.71 and 1.97 cm⁻¹) decreased linearly with increasing pressure at the rates −0.009(2), −0.077(3) and −0.034(2) cm⁻¹/kbar, respectively. Possible mechanisms of the observed pressure effects are discussed. For further studies of linewidth variations with the pressure, gaseous helium as a best possible high-pressure medium is strongly recommended.     

CO2-broadened water in the pure rotation and ν2 fundamental regions

The CO₂-broadened water coefficients (half-widths, line shifts, and temperature dependence of the widths) are predicted using a fully complex Robert-Bonamy formulation for the 937 allowed and forbidden perpendicular type transitions of (000)-(000) between 200 and 900 cm⁻¹ in order to facilitate atmospheric remote sensing of Mars and Venus. In addition, empirical Lorentz line widths and pressure-induced frequency-shifts of CO₂-broadened H₂¹⁶O are obtained at room temperature for 257 perpendicular transitions of the (010)-(000) fundamental. For this, calibrated spectra recorded at 0.0054 cm⁻¹ resolution are measured assuming Voigt line shapes. For transitions between 1287 and 1988 cm⁻¹ with rotational quanta up to J = 13 and K_a = 6, the widths vary from 0.045 to 0.212 cm⁻¹ atm⁻¹ at 300 K; the pressure-shifts are quite large and range from −0.0386 to +0.0436 cm⁻¹ atm⁻¹. For the (010)-(000) band, the RMS and mean observed and calculated differences for CO₂-broadened H₂O half-widths are 12% and −1.9%, respectively, while the RMS and mean ratios of the observed and calculated pressure-induced shift coefficients are 1.6 and 0.79, respectively. For pairs of transitions involving K_a = 0 and 1, such as 2_0 2 ← 3_1 3 and 3_1 3 ← 2_0 2, both the calculated and observed pressure induced shifts in positions are opposite in sign and often similar in magnitude. The data are too limited to characterize vibrational dependencies of the widths, however.     

Coherence-converted population transfer FTMW-IR double resonance spectroscopy of CH3OD in the OD-stretch region

Rotationally selected infrared spectra of jet-cooled CH₃OD have been recorded and analyzed in the OD-stretch region (2710-2736 cm⁻¹). The observed spectra are obtained by monitoring three E-species microwave transitions (1₋₁ ← 1₀ at 18.957 GHz, 2₋₁ ← 2₀ at 18.991 GHz, and 3₋₁ ← 3₀ at 19.005 GHz) in a narrowband cavity Fourier transform microwave spectrometer, using the background-free coherence-converted population transfer technique. Of the four upper state subbands observed, two (K′ = 0 and −2) are split by perturbations. The E-species deperturbed band origin is at 2718.1 cm⁻¹. The deperturbed reduced term values follow a pattern similar to the ground state. This allows the J′ = 0 torsional tunneling splitting to be estimated as 2.1 cm⁻¹, which can be compared to 2.6 cm⁻¹ in the ground state.     

Global modeling of CO2 absolute line intensities from CW-CRDS and FTS measurements in the 1.6 and 2.0 μm regions

Line intensities of ¹³C¹⁶O₂ have been measured between 5851 and 6580 cm⁻¹ using CW-cavity ring down spectroscopy (CRDS) and in the 4700-5050 and 6050-6850 cm⁻¹ regions using Fourier transform spectroscopy. As a result of the high sensitivity (noise equivalent absorption α_min∼3×10⁻¹⁰ cm⁻¹) and high dynamics allowed by CW-CRDS, accurate line intensities of 2039 transitions ranging between 1.1×10⁻²⁸ and 1.3×10⁻²³ cm⁻¹/(molecule cm⁻²) were measured with an average accuracy of 4%. These transitions belong to a total of 48 bands corresponding to the ΔP=9 series of transitions. Additionally, unapodized absorption spectra of ¹³C-enriched samples have been recorded using a high-resolution Bruker IFS125HR Fourier transform spectrometer. Spectral resolutions of 0.004 cm⁻¹ (maximum optical path difference (MOPD)=225 cm) and 0.007 cm⁻¹ (MOPD=128.6 cm), and pressure×path length products in the ranges 5.2-12 and 69-450 hPa×m have been used for the lower and higher energy spectral regions, respectively. Absolute line intensities have been measured in the 2001i−00001, 3001i−00001 (i=1, 2, 3) and 00031−00001 bands. An excellent agreement was achieved for the line intensities of the 3001i−00001 (i=1, 2, 3) bands measured by both FTS and CW-CRDS. The CW-CRDS and FTS experimental intensity data together with selected intensity information from the literature have been fitted simultaneously using the effective operators approach. Two sets of effective dipole moment parameters have thus been obtained, which reproduce the observed line intensities in the 2.0 and 1.6 μm regions within experimental uncertainties.     

A multispectrum analysis of the ν2 band of HCN: Part I. Intensities, broadening, and shift coefficients

Absolute intensities, self- and air-broadening coefficients, self- and air-induced shift coefficients and their temperature dependences have been determined for lines belonging to the P- and R-branches of the ν₂ band of H¹²C¹⁴N centered near 712 cm⁻¹. Infrared spectra of HCN in the 14-μm region were obtained at high resolution (0.002-0.008 cm⁻¹) using two different Fourier transform spectrometers (FTS), the McMath-Pierce FTS at the National Solar Observatory on Kitt Peak and the Bruker IFS 120HR FTS at the Pacific Northwest National Laboratory. Spectra were recorded with 99.8% pure HCN as well as lean mixtures of HCN in air at various temperatures ranging between +26 and −60 °C. A multispectrum nonlinear least squares technique was used to fit selected intervals of 36 spectra simultaneously to obtain the line positions, intensities, broadening, and shift parameters. The measured line intensities were analyzed to determine the vibrational band intensity and the Herman-Wallis coefficients. The measured self-broadening coefficients vary between 0.2 and 1.2 cm⁻¹ atm⁻¹ at 296 K, and the air-broadening coefficients range from 0.08 to 0.14 cm⁻¹ atm⁻¹ at 296 K. The temperature dependence exponents of self-broadening range from 1.46 to −0.12 while the corresponding exponents for air broadening vary between 0.58 and 0.86. The present measurements are the first known determination of negative values for the temperature dependence exponents of HCN-broadening coefficients. We were able to support our self-broadening measurements with appropriate theoretical calculations. Our present measurements are compared, where possible, with previous measurements for this and other HCN bands, as well as the parameters that are included in the 2000 and 2004 editions of the high-resolution transmission (HITRAN) database.     

Intensities and widths of H2O lines between 1800 and 2100 cm-1

A non-linear, least-squares program was used to obtain the line intensities and widths of 91 air-broadened lines in the ν₂ rotation-vibration band of water vapor in the region from 1800 to 2100 cm^-1. The values obtained for the line intensities are, on the average, about 7% stronger than the Air Force Cambridge Research Laboratories (AFCRL) Atmospheric Absorption Line Parameters Compilation. The experimental values for the half widths of the H₂O lines are, on the average, 4% higher than the calculated AFCRL values. The measurements have confirmed the narrow widths of some high J transition lines measured by tunable diode laser spectroscopy.     

Self-broadening coefficients in the ν7 band of ethylene at room and low temperatures

Using a tunable diode-laser spectrometer, we have measured self-broadening coefficients for a few transitions in the ν₇ fundamental band of C₂H₄ at 298 and 174 K. The studied transitions J^′, K_a^′, K_c^′←J, K_a, K_c with 3?J?17, 1?K_a?4, and 1?K_c?14 are located in the spectral range 919-982 cm⁻¹. The collisional widths are measured by fitting each spectral line with Voigt, Rautian, and speed-dependent Rautian profiles. The latter model provides larger broadening coefficients than the Rautian profile and still larger coefficients than the Voigt profile. An approximate semiclassical calculation performed by considering only electrostatic interactions leads to reasonable agreement with the experimental data. By comparing the results obtained at room and low temperatures, the temperature dependence of the self-broadening has been determined both experimentally and theoretically.     

Doppler-limited CW infrared cavity ringdown spectroscopy of the ν1+ν3 OH + CH stretch combination band of jet-cooled methanol

A high resolution cavity ringdown spectrometer (CRDS) has been constructed using a 1.5 μm continuous-wave external-cavity tunable diode laser, a mode-matched near-confocal ringdown cavity, and 2 cm pulsed slit jet. Without signal averaging, the RMS noise in the absorption signal is 1.7 × 10⁻⁹ cm⁻¹. The rotationally resolved overtone spectrum of the OH(ν₁) + CH(ν₃) stretch combination band of methanol between 6510 and 6550 cm⁻¹ has been observed for J^′=0-8 and K^′=0-3 at sub-Doppler resolution. In total, 418 lines are assigned and global fits yield molecular torsion-rotation parameters for the upper state. Four K^′-localized perturbations are analyzed and the pattern of residuals is discussed.     

The absorption spectrum of phosphine (PH3) between 2.8 and 3.7 μm: Line positions, intensities, and assignments

Over 8000 line positions and intensities of phosphine (PH₃) at 3 μm have been measured at 0.0115 cm⁻¹ resolution with the McMath-Pierce Fourier Transform spectrometer at Kitt Peak. The observed line intensities ranged from 4.13 × 10⁻⁶ to 4.69 × 10⁻² cm⁻² atm⁻¹ at 296 K, for line positions between 2724.477 and 3601.652 cm⁻¹. This region spans eight interacting vibrational states: 3ν₂ (2940.8 cm⁻¹), 2ν₂ + ν₄ (3085.6 cm⁻¹), ν₂ + 2ν₄ (3214.9 cm⁻¹), ν₁ + ν₂ (3307.6 cm⁻¹), ν₂ + ν₃ (3310.5 cm⁻¹), 3ν₄ (∼3345 cm⁻¹), ν₁ + ν₄ (3426.9 cm⁻¹), and ν₃ + ν₄ (3432.9 cm⁻¹). Assignments have been determined for all the bands except 3ν₄ (a weak band in a highly congested area) for a total of 4232 transitions. The total integrated intensity for this region is 5.70 cm⁻² atm⁻¹ near 296 K, and assigned lines account for 79% of the observed absorption. The two strongest bands in the region are ν₁ + ν₄ and ν₃ + ν₄ with band strengths at 296 K of 1.61 and 2.01 cm⁻² atm⁻¹, respectively. An empirical database of PH₃ line parameters (positions, intensities, and assignments) is now available. Lower state energies (corresponding to assignments from this study) and line widths from the literature are included; default values are used for unassigned features.     

High-resolution FTIR measurement of the 2ν8 band of methylene fluoride (CH2F2)

A high-resolution (0.003 cm⁻¹) infrared absorption spectrum of the first overtone of the fundamental mode ν₈ of methylene fluoride (CH₂F₂) has been measured on a Bruker IFS 120-HR Fourier transform infrared spectrometer. More than 2000 ro-vibration transitions in the range of 2770-2900 cm⁻¹ with J ? 45 and K_a ? 20 have been assigned in this B-type band centered at 2838.5 cm⁻¹. Precise value for the band origin (2838.579799 cm⁻¹) and centrifugal distortion constants up to third order (Φ_JK, Φ_KJ, and Φ_K) have been obtained by fitting a total of 1474 unblended ro-vibration transitions (J ? 45 and K_a ? 13) of the 2ν₈ band with a standard deviation of 0.00029 cm⁻¹ using a Watson’s A-reduced Hamiltonian in the I^r representation. Signature of perturbations with nearby states has been seen.     

High-resolution infrared spectra of bicyclo[1.1.1]pentane

Infrared spectra of bicyclo[1.1.1]pentane (C₅H₈) have been recorded at a resolution (0.0015 cm⁻¹) sufficient to resolve for the first time individual rovibrational lines. This initial report presents the ground state constants for this molecule determined from the detailed analysis of three of the ten infrared-allowed bands, ν₁₄(e′) at 540 cm⁻¹, ν₁₇ (a₂″) at 1220 cm⁻¹, ν₁₈(a₂″) at 832 cm⁻¹, and a partial analysis of the ν₁₁(e′) band at 1237 cm⁻¹. The upper states of transitions involving the lowest frequency mode, ν₁₄(e′), show no evidence of rovibrational perturbations but those for the ν₁₇ and ν₁₈ (a₂″) modes give clear indication of Coriolis coupling to nearby e′ levels. Accordingly, ground state constants were determined by use of the combination-difference method for all three bands. The assigned frequencies provided over 3300 consistent ground state difference values, yielding the following constants for the ground state (in units of cm⁻¹): B₀ = 0.2399412(2), D_J = 6.024(6) × 10⁻⁸, D_JK = −1.930(21) × 10⁻⁸. For the unperturbed ν₁₄(e′) fundamental, more than 3500 transitions were analyzed and the band origin was found to be at 540.34225(2) cm⁻¹. The numbers in parentheses are the uncertainties (two standard deviations) in the values of the constants. The results are compared with those obtained previously for [1.1.1]propellane and with those computed at the ab initio anharmonic level using the B3LYP density functional method with a cc-pVTZ basis set.     

Measurements and theoretical calculations of self-broadening and self-shift coefficients in the ν2 band of CH3D

In this paper, we report measured Lorentz self-broadening and self-induced pressure-shift coefficients of ¹²CH₃D in the ν₂ fundamental band (ν₀ ≈ 2200 cm⁻¹). The multispectrum fitting technique allowed us to analyze simultaneously seven self-broadened absorption spectra. All spectra were recorded at the McMath-Pierce Fourier transform spectrometer of the National Solar Observatory (NSO) on Kitt Peak, AZ with an unapodized resolution of 0.0056 cm⁻¹. Low-pressure (0.98-2.95 Torr) as well as high-pressure (17.5-303 Torr) spectra of ¹²C-enriched CH₃D were recorded at room temperature to determine the pressure-broadening coefficients of 408 ν₂ transitions with quantum numbers as high as J″ = 21 and K = 18, where K″ = K′ ≡ K (for a parallel band). The measured self-broadening coefficients range from 0.0349 to 0.0896 cm⁻¹ atm⁻¹ at 296 K. All the measured pressure-shifts are negative. The reported pressure-induced self-shift coefficients vary from about −0.004 to −0.008 cm⁻¹ atm⁻¹. We have examined the dependence of the measured broadening and shift parameters on the J″, and K quantum numbers and also developed empirical expressions to describe the broadening coefficients in terms of m (m = −J″, J″, and J″ + 1 in the ^QP-, ^QQ-, and ^QR-branch, respectively) and K. On average, the empirical expressions reproduce the measured broadening coefficients to within 3.6%. A semiclassical theory based upon the Robert-Bonamy formalism of interacting linear molecules has been used to calculate these self-broadening and self-induced pressure-shift coefficients. In addition to the electrostatic interactions involving the octopole and hexadecapole moments of CH₃D, the intermolecular potential includes also an atom-atom Lennard-Jones model. For low K (K ? 3) with |m| ? 8 the theoretical results of the broadening coefficients are in overall good agreement (3.0%) with the experimental data. For transitions with K approaching |m|, they are generally significantly underestimated (8.8%). The theoretical self-induced pressure shifts, whose vibrational contribution is derived from results in the ^QQ-branch, are generally smaller in magnitude than the experimental data in the ^QP-, and ^QR-branches (15.2%).     

Nuclear hyperfine structure in the XΣ state of ZrC

Electronic band systems of zirconium monocarbide, ZrC, in the 16 000-19 000 cm⁻¹ region have been observed following the reaction of laser-ablated Zr atoms with methane under supersonic free-jet conditions. Rotational analyses of high-resolution spectra have shown that the ground state of ZrC is a ³Σ state, with r₀=1.8066 Å and an unexpectedly small spin-spin parameter, λ=0.5139 cm⁻¹. The spectra are dense because of the five naturally occurring isotopes of Zr. Four of these, with mass numbers 90, 92, 94, and 96, have I=0, but the fifth, ⁹¹Zr, present in 11.22% abundance, has I=5/2. Lines of ⁹¹ZrC can be assigned in some of the strongest bands, and are found to display sizeable hyperfine splittings, with widths of up to 0.2 cm⁻¹. Analysis shows that the largest hyperfine effects are in the ground state, where b=−0.03133±0.00015 cm⁻¹ and c=−0.00123±0.00037 cm⁻¹ (3σ error limits). The large Fermi contact parameter, b, indicates that an unpaired Zr 5sσ electron is present, which, taken together with the small value of λ, means that the ground state must be a ³Σ⁺ state, from the electron configuration (Zr 5sσ)¹ (C 2pσ)¹. Internal hyperfine perturbations occur between the F₁ and F₃ electron spin components of the ground state in the range N=2-4, producing extra lines in some of the branches; the perturbations are of the type ΔN=0, ΔJ=±2, and are a second-order effect arising because the F₁ (J=N+1) and F₃ (J=N−1) spin components both interact with the F₂ (J=N) component through ΔN=0, ΔJ=±1 matrix elements of the Fermi contact operator. Second-order perturbations of this type can only occur in states that are very close to case (b) coupling.     

Collisional broadening and line intensities in the ν2 and ν4 bands of PH3

Using a tunable diode-laser spectrometer self-broadening coefficients and absolute intensities have been measured for 26 lines of PH₃ at 298 K in the QR branch of the ν₂ band and the PP and RP branches of the ν₄ band. The recorded lines with J values ranging from 2 to 14 and K from 0 to 11 are located in the spectral range 995-1093 cm⁻¹. Self-broadening coefficients have also been measured at 173.4 K for nine of these lines. The collisional widths and line strengths are obtained by fitting each spectral line with different theoretical profiles. The results obtained for the line intensities are in good agreement with recent measurements [J. Mol. Spectrosc. 215 (2002) 178]. The self-broadening coefficients are also calculated on the basis of a simple semiclassical model involving only the electrostatic interactions. A satisfactory agreement is obtained except for high J values or K values equal to J, for which the calculated results are notably underestimated. By comparing broadening coefficients at room and low temperatures, the temperature dependence of these broadenings has been determined both experimentally and theoretically.     

Self-broadened line parameters for water vapour in the spectral region 5000-5600 cm

The self-broadening coefficients and intensities of approximately 460 of the strongest water vapour lines (intensity S ? 1.5 × 10⁻²³ cm molec⁻¹) in the spectral region 5000-5600 cm⁻¹ have been derived from new laboratory measurements. The derived line intensities are on average in a good agreement with those in HITRAN-2001 (v.11.0) (within 0.5% for total band intensity). Self-broadening coefficients are compared with values estimated from the HITRAN-2001 foreign-broadening coefficients. Comparison has been also made with the recent HITRAN-2004 (v.12.0) compilation, which revealed marked systematic differences in the self-broadening coefficients (up to 20%) and in the line intensities (up to 5%). The possible reasons for these deviations are discussed.     

Room-temperature broadening and pressure-shift coefficients in the ν2 band of CH3D-O2: Measurements and semi-classical calculations

We report measured Lorentz O₂-broadening and O₂-induced pressure-shift coefficients of CH₃D in the ν₂ fundamental band. Using a multispectrum fitting technique we have analyzed 11 laboratory absorption spectra recorded at 0.011 cm⁻¹ resolution using the McMath-Pierce Fourier transform spectrometer, Kitt Peak, Arizona. Two absorption cells with path lengths of 10.2 and 25 cm were used to record the spectra. The total sample pressures ranged from 0.98 to 339.85 Torr with CH₃D volume mixing ratios of 0.012 in oxygen. We report measurements for O₂ pressure-broadening coefficients of 320 ν₂ transitions with quantum numbers as high as J″ = 17 and K = 14, where K″ = K′ ≡ K (for a parallel band). The measured O₂-broadening coefficients range from 0.0153 to 0.0645 cm⁻¹ atm⁻¹ at 296 K. All the measured pressure-shifts are negative. The reported O₂-induced pressure-shift coefficients vary from about −0.0017 to −0.0068 cm⁻¹ atm⁻¹. We have examined the dependence of the measured broadening and shift parameters on the J″, and K quantum numbers and also developed empirical expressions to describe the broadening coefficients in terms of m (m = −J″, J″, and J″ + 1 in the ^QP-, ^QQ-, and ^QR-branch, respectively) and K. On average, the empirical expressions reproduce the measured broadening coefficients to within 4.4%. The O₂-broadening and pressure shift coefficients were calculated on the basis of a semiclassical model of interacting linear molecules performed by considering in addition to the electrostatic contributions the atom-atom Lennard-Jones potential. The theoretical results of the broadening coefficients are generally larger than the experimental data. Using for the trajectory model an isotropic Lennard-Jones potential derived from molecular parameters instead of the spherical average of the atom-atom model, a better agreement is obtained with these data, especially for |m| ? 12 values (11.3% for the first calculation and 8.1% for the second calculation). The O₂-pressure shifts whose vibrational contribution are either derived from parameters fitted in the ^QQ-branch of self-induced shifts of CH₃D or those obtained from pressure shifts induced by Xe in the ν₃ band of CH₃D are in reasonable agreement with the scattered experimental data (17.0% for the first calculation and 18.7% for the second calculation).     

Measurements and theoretical calculations of N2-broadening and N2-shift coefficients in the ν2 band of CH3D

In this paper, we report measured Lorentz N₂-broadening and N₂-induced pressure-shift coefficients of CH₃D in the ν₂ fundamental band using a multispectrum fitting technique. These measurements were made by analyzing 11 laboratory absorption spectra recorded at 0.0056 cm⁻¹ resolution using the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory on Kitt Peak, Arizona. The spectra were obtained using two absorption cells with path lengths of 10.2 and 25 cm. The total sample pressures ranged from 0.98 to 402.25 Torr with CH₃D volume mixing ratios of 0.01 in nitrogen. We have been able to determine the N₂ pressure-broadening coefficients of 368 ν₂ transitions with quantum numbers as high as J″ = 20 and K = 16, where K″ = K′ ≡ K (for a parallel band). The measured N₂-broadening coefficients range from 0.0248 to 0.0742 cm⁻¹ atm⁻¹ at 296 K. All the measured pressure-shifts are negative. The reported N₂-induced pressure-shift coefficients vary from about −0.0003 to −0.0094 cm⁻¹ atm⁻¹. We have examined the dependence of the measured broadening and shift parameters on the J″, and K quantum numbers and also developed empirical expressions to describe the broadening coefficients in terms of m (m = −J″, J″, and J″ + 1 in the ^QP-, ^QQ-, and ^QR-branch, respectively) and K. On average, the empirical expressions reproduce the measured broadening coefficients to within 4.7%. The N₂-broadening and pressure-shift coefficients were calculated on the basis of a semiclassical model of interacting linear molecules performed by considering in addition to the electrostatic contributions the atom-atom Lennard-Jones potential. The theoretical results of the broadening coefficients are in good overall agreement with the experimental data (8.7%). The N₂-pressure shifts whose vibrational contribution is derived from parameters fitted in the ^QQ-branch of self-induced shifts of CH₃D, are also in reasonable agreement with the scattered experimental data (20% in most cases).     

Near-infrared Fourier-transform and millimeterwave spectra of the BiS radical

This paper reports the 6400-7400 cm⁻¹ Fourier-transform (FT) near-infrared (NIR) emission spectrum of the BiS X₂²Π_3/2 → X₁²Π_1/2 fine structure bands as well as the millimeterwave rotational spectrum of the X₁²Π_1/2 state. For the FTNIR observations, BiS was produced by reaction of bismuth with sulfur vapor and excited by energy transfer from metastable oxygen, O₂(a¹Δ_g), in a fast-flow system. As was the case for BiO [O. Shestakov, R. Breidohr, H. Demes, K.D. Setzer, E.H. Fink, J. Mol. Spectrosc. 190 (1998) 28-77], the 0.5 cm⁻¹resolution spectrum revealed a number of strong bands in the Δv = 0 and ±1 sequences which showed perturbed band spacings, band shapes, and intensities due to avoided crossing of the X₂²Π_3/2 and A₁⁴Π_3/2 potential curves for v^′ ? 4 of X₂²Π_3/2. The millimeterwave rotational spectrum of BiS in its X₁²Π_1/2 state was observed when BiS was produced in a high-temperature oven by a discharge in a mixture of Bi vapor and CS₂. The signal to noise ratio was markedly improved by using a White-type multipath cell. Ninety seven features from J′ = 23.5 to J′ = 41.5 were measured between 150 and 300 GHz. Analysis of the 0.5 cm⁻¹ resolution FT spectrum yielded the fine structure splitting and vibrational constants of the states. A simultaneous analysis of millimeterwave and a 0.005 cm⁻¹ FT spectrum of the 0-0 band of the NIR system was carried out to give precise rotational, fine, and hyperfine constants for the X₁²Π_1/2 and X₂²Π_3/2 states. The results are consistent with those reported earlier for BiO and indicate only a slight decrease in the unpaired electron density in the 6p(π^∗) orbital on the Bi atom.