The Lamb-dip spectrum of phosphine: The nuclear hyperfine structure due to hydrogen and phosphorus

For the first time, the hyperfine structure of the rotational J = 1 ← 0 (K = 0) and J = 2 ← 1 (K = 0, 1) transitions of phosphine has been resolved by using microwave spectroscopy. To this purpose, the Lamb-dip technique has been employed. In addition, the J = 3 ← 2 (K = 0, 1, 2) transition has been recorded at Doppler resolution. The present investigation allowed us to provide accurate values for most of the hyperfine constants as well as ground state rotational parameters.     

The Lamb-dip spectrum of the J + 1 ← J (J = 0, 1, 3-8) transitions of HCN: The nuclear hyperfine structure due to H, C, and N

The pure rotational J + 1 ← J transitions, with J = 0, 1, 3-8, of H¹³CN have been observed in the millimeter- and submillimeter-wave region using the Lamb-dip technique to resolve the hyperfine structure due to H, ¹³C, and ¹⁴N. The present observations allow us to provide for the first time the spin-rotation constant of ¹³C and the spin-spin interaction constant S₁₂ (between H and ¹³C) as well as to remarkably improve the quadrupole coupling and spin-rotation constants of ¹⁴N. In addition, a good empirical estimation of C_I(H), based on ab initio calculations, has also been provided. Furthermore, our frequencies together with previous data permit to determine the most accurate ground state rotational parameters known up to now.     

Sub-Doppler and Doppler spectroscopy of DCN isotopomers in the terahertz region: ground and first excited bending states (v1v2v3)=(0 1 0)

The rotational spectra of the deuterium cyanide isotopic species DCN, D¹³CN, DC¹⁵N, and D¹³C¹⁵N were recorded in the vibrational ground and first excited bending state (v₂=1) up to 2 THz. The R-branch transitions from J=3←2 to J=13←12 were measured with sub-Doppler resolution. These very high resolution (∼70 kHz) and precise (±3-10 kHz) saturation dip measurements allowed for resolving the underlying hyperfine structure due to the ¹⁴N nucleus in DCN and D¹³CN for transitions as high as J=10←9. Additional high JR-branch (J=25←24 to J=28←27) transitions around 2 THz and direct l-type (ΔJ=0, J=19 to J=25) transitions from 66 to 118 GHz were recorded in Doppler-limited resolution. For the ground state of D¹³C¹⁵N, the J=1←0 transition was measured for the first time. The transition frequency accuracies for the other deuterated species were significantly improved. These new experimental data, together with the available infrared rovibrational data and previously measured direct l-type transitions, were subjected to a global least squares analysis for each isotopomer. This yielded precise sets of molecular constants for the ground and first excited vibrational states, including the nuclear quadrupole and magnetic spin-rotation coupling constants of the ¹⁴N nucleus for DCN and D¹³CN. The hyperfine structure due to the D, ¹³C, and ¹⁵N nuclei have not been resolved, but led to a broadening of the observed saturation dips.     

Hyperfine structure of the J=1←0 transition of HCl and HCl: improved ground state parameters

The pure rotational J=1←0 transitions of H³⁵Cl and H³⁷Cl have been observed in the millimeter-wave region using the Lamb-dip technique to resolve the hyperfine structure due to ³⁵Cl or ³⁷Cl and H. The present observations allow to provide not only very accurate hyperfine constants but also, joint together with previous data, the most accurate ground state rotational parameters known up to now. The experimental determination of the hyperfine parameters has also been supported by ab initio computations.     

Doppler-limited rotational spectrum of the NH radical in the 2 THz region

The Doppler-limited rotational spectrum of the NH radical in its electronic (X) and vibrational ground state has been measured using the frequency stabilized Cologne side-band spectrometer in the frequency region near 2 THz. The nitrogen ¹⁴N nuclear hyperfine patterns have been observed accompanying the resolved fine (J^′←J″) structure of the N=2←1 rotational transition. The observed peak frequencies were analyzed in detail together with the previously measured hyperfine frequencies of the N=1←0 rotational transition and with combination differences obtained from the high-resolution electronic spectra to derive precise rotational, centrifugal distortion, fine, and hyperfine parameters. In the numerical analysis the essential attention has been paid to partly resolved and unresolved hyperfine structures. The peak positions of the partly or fully overlapped lines were analyzed with the help of a profile simulation with estimated half-widths and calculated relative intensities and in this manner the least square fit of the unresolved and partly resolved lines was significantly improved. The NH radical is an extremely important species in nitrogen chemical reaction networks in the interstellar medium and atmospheric chemistry.     

Improved ground state rotational parameters of deuterium fluoride, DF

The rotational spectrum of DF in the 1.3-3.3 THz frequency region has been observed by means of a tunable far-infrared spectrometer. The J + 1 ← J, with J = 1-4, rotational transitions of DF have been recorded with an accuracy of the order of 50-200 kHz. These measurements, in conjunction with the hyperfine components of the J = 1 ← 0 transition recently observed [Cazzoli and Puzzarini, J. Mol. Spectrosc. 231 (2005) 124-130] and the rotational transitions up to J = 47 [R.S. Ram, Z. Morbi, B. Guo, K.-Q. Zhang, P.F. Bernath, J. Vander Auwera, J.W.C. Johns, S.P. Davies, Astrophys. J. Suppl. Series 103 (1996) 247-254] consented to improve the ground state rotational parameters of DF.     

Lineshape analysis of the J = 3 ← 2 and J = 5 ← 4 rotational transitions of room temperature CO broadened by N2, O2, CO2 and noble gases

Collisional relaxation has been considered for millimeter lines of carbon monoxide at room temperature. Accurate measurements of carbon dioxide- and rare gases-broadened widths have been performed on the J = 3 ← 2 rotational line of ¹²CO by using a video-type spectrometer. Measurements of nitrogen-, oxygen-, and xenon-broadened widths of the J = 5 ← 4 rotational line of ¹³CO were also carried by using a frequency-modulated spectrometer. A lineshape study performed on all the investigated binary systems provide confirmation that Voigt profile is not a suitable model to analyse experimental lines in the millimeter-waves region. On one hand, using this profile in the low pressure range, i.e. in the Doppler regime, the retrieved collisional linewidths do not follow a linear variation with the perturbing gas pressure. On the other hand, regardless of the pressure, lineshapes exhibit a narrowed profile. An accurate analysis of the pressure dependence of relaxation rates show that the Galatry profile is not appropriate and that experimental lineshapes are actually Speed Dependent Voigt profiles. Accurate broadening parameters were retrieved from this profile and compared to previous reported values and predictions calculated from the Robert-Bonamy formalism. Finally a variation of the ratio of relaxation speed dependence to broadening parameters versus relative masses of the collision partners is presented.     

Rotational levels of the (0 0 0) and (0 1 0) states of D2O from hot emission spectra in the 320-860 cm region

The far-infrared emission spectra of deuterated water vapour were measured at different temperatures (1370, 1520, and 1950 K) in the range 320-860 cm⁻¹ at a resolution of 0.0055 cm⁻¹. The measurements were performed in an alumina cell with an effective length of hot gas of about 50 cm. More than 1150 new measured lines for the D₂¹⁶O molecule corresponding to transitions between highly excited rotational levels of the (0 0 0) and (0 1 0) vibrational states are reported. These new lines correspond to rotational states with higher values of the rotational quantum numbers compared to previously published determinations: J_max=26 and for the (0 0 0) ← (0 0 0) band, J_max=25 and for the (0 1 0) ← (0 1 0) band, and J_max=26 and for the (0 1 0) ← (0 0 0) band. The estimated accuracy of the measured line positions is 0.0005 cm⁻¹. To our knowledge no experimentally measured rotational transitions for D₂¹⁶O within an excited vibrational state have been available in the literature so far. An extended set of experimental rotational energy levels for (0 0 0) and (0 1 0) vibration states including all previously available data has been determined. For the data reduction we used the generating function model. The root mean square (RMS) deviation between observed and calculated values is 0.0012 cm⁻¹ for 692 rotational levels of the (0 0 0) state and 0.0010 cm⁻¹ for 639 rotational levels of the (0 1 0) vibrational state. A comparison of the observed energy levels with the best available values from the literature and with the global predictions from molecular electronic potential energy surface [J. Chem. Phys. 106 (1997) 4618] for the (0 0 0) and (0 1 0) states is discussed.     

Quantum interferences from cross talk in J = 1/2 ↔ J = 1/2 transitions

We consider the possibility of a control field opening up multiple pathways and thereby leading to new interference and coherence effects. We illustrate the idea by considering the J = 1/2 ↔ J = 1/2 transition. As a result of the additional pathways, we show the possibilities of nonzero refractive index without absorption and gain without inversion. We explain these results in terms of the coherence produced by the opening of an extra pathway.     

New assignments, line intensities, and HITRAN database for CH3OH at 10 μm

The Fourier transform spectrum of CH₃OH in the 10 μm region has been re-examined at higher pressure and path length than heretofore, as part of a program to provide comprehensive CH₃OH spectral data for astrophysical and atmospheric applications. With the increase in spectral sensitivity, it has been possible to assign new torsionally excited ν₁₂=1 and ν₁₂=2 subbands plus further high-K, ν₁₂=0 subbands of the ν₈ CO-stretching band. Upper-state term values have been determined, and have been fitted to J(J+1) power-series expansions in order to obtain the excited ν₈ substate origins. A variety of weaker subbands from other modes has also been identified in the 10 μm spectrum including ν₁₂=0, ν₁₂=1, and ν₁₂=0←1 torsional subbands of the ν₇ in-plane CH₃ rock, ν₁₂=0←1 and ν₁₂=0←2 torsional combination subbands of the ν₆ OH bend, and ν₁₂=0←2 subbands of the ν₅ symmetric CH₃ bend. Line intensities have been retrieved line-by-line from the spectra. A large set of “unperturbed” ν₈ transitions has been modeled using the same type of multi-parameter effective Hamiltonian employed successfully for the ground state, with inclusion of the intensities of a subset of the stronger ν₈ spectral lines in the fitting in order to obtain appropriate transition dipole terms. Together, a 10 μm methanol database in HITRAN format has been generated.     

N2-, H2-, and He-induced collisional broadening of the J = 24 ← 23 transition of HC3N located near 218.3 GHz at different temperatures

We report on experimental collisional relaxation of the J = 24 ← 23 line of HC₃¹⁴N, located near 218.3 GHz, induced by nitrogen, hydrogen, and helium. The measurements were carried out at selected temperatures in the 235-350 K range using a video-type spectrometer. The foreign gas broadening parameters and their temperature dependences were determined assuming Voigt lineshape profiles and the usual T⁻ⁿ temperature law. The experimental broadening parameters are compared with results derived using the ATC collisional formalism.     

Line mixing and speed dependence in CO2 at 6227.9 cm: Constrained multispectrum analysis of intensities and line shapes in the 30013 ← 00001 band

Line position, intensity and line shape parameters (Lorentz widths, pressure shifts, line mixing, speed dependence) are reported for transitions of the 30013 ← 00001 band of ¹⁶O¹²C¹⁶O (ν₀ = 6227.9 cm⁻¹). The results are determined from 26 high-resolution, high signal-to-noise ratio spectra recorded at room temperature with the McMath-Pierce Fourier transform spectrometer. To minimize the systematic errors of the retrieved parameters, we constrained the multispectrum nonlinear least squares retrieval technique to use quantum mechanical expressions for the rovibrational energies and intensities rather than retrieving the individual positions and intensities line by line. Self- and air-broadened Lorentz width and pressure-induced shift, speed dependence and line mixing (off-diagonal relaxation matrix elements) coefficients were adjusted individually. Errors were further reduced by simultaneously fitting the interfering absorptions from the weak 30012 ← 00001 band of ¹⁶O¹³C¹⁶O as well as the weak hot bands 31113 ← 01101, 32213 ← 02201, 40014 ← 10002 and 40013 ← 10001 of ¹⁶O¹²C¹⁶O in this spectral window. This study complements our previous work on line mixing and speed dependence in the 30012 ← 00001 band (ν₀ = 6347.8 cm⁻¹) [V.M. Devi, D.C. Benner, L.R. Brown, C.E. Miller, R.A. Toth, J. Mol. Spectrosc. 242 (2007) 90-117] and provides key data needed to improve atmospheric remote sensing of CO₂.     

Analysis of the first triad of interacting states (0 2 0), (1 0 0), and (0 0 1) of D2O from hot emission spectra

The far-infrared and middle-infrared emission spectra of deuterated water vapour were measured at temperatures 1370, 1520, and 1940 K in the ranges 320-860 and 1750-3400 cm⁻¹. The measurements were performed in an alumina cell with an effective length of hot gas of about 50 cm. More than 3550 new measured lines for the D₂¹⁶O molecule corresponding to transitions from highly excited rotational levels of the (0 2 0), (1 0 0), and (0 0 1) vibrational states are reported. These new lines correspond to rotational states with higher values of the rotational quantum numbers compared to previously published determinations: J_max = 29 and K_a(max) = 22 for the (0 2 0) state, J_max = 29 and K_a(max) = 25 for the (1 0 0) state, and J_max = 30 and K_a(max) = 23 for the (0 0 1) state. The extended set of 1987 experimental rotational energy levels for the (0 2 0), (1 0 0), and (0 0 1) vibration states including all previously available data has been determined. For the data reduction we used the generating function model. The root mean square (RMS) deviation between observed and calculated values is 0.004 cm⁻¹ for 1952 rovibrational levels of all three vibration states. A comparison of the observed energy levels with the best available values from the literature and with the global predictions from molecular electronic potential energy surfaces of water isotopic species [H. Partridge, D.W. Schwenke, J. Chem. Phys. 106 (1997) 4618] is discussed. The latter confirms a good consistency of mass-dependent DBOC corrections in the PS potential function with new experimental rovibrational data.     

Rotational spectrum of the v11 = 1 and v14 = 1 vibrational states of CH3CCCCH

The pure rotational spectra of the v₁₁ = 1 and v₁₄ = 1 vibrational states of the main isotopic species of methyldiacetylene have been recorded and assigned in the 80-400 GHz frequency range, spanning the quantum numbers 19 ? J ? 95 and 0 ? K ? 15. The present study allows us to provide accurate rotational, centrifugal distortion and vibration-rotation interaction constants. The experimental investigation has been strongly supported by quantum-chemical computations at the second-order Møller-Plesset theory (MP2) in conjunction with a triple-zeta quality basis set.     

A Comparison of Lineshape Models in the Analysis of Modulated and Natural Rotational Line Profiles: Application to the Pressure Broadening of OCS and CO

We report on the self and pressure broadening of the J=9←8 transition of O¹²CS and O¹³CS and the J+1←J, with J=0, 1, 2, 3, rotational transitions of ¹²CO and ¹³CO. In particular, the J=9← 8 of OCS and J=1← 0 of CO have been investigated for a detailed comparison of lineshape models in the analysis of natural and modulated line profiles. Since the frequency modulation technique improves the instrumental sensitivity, allowing the study of weak transition line profiles, a thorough test of this technique applied to lineshape analysis has been carried out. Finally, the self and pressure broadening coefficients are also given. Due to the important role covered by CO in the atmospheric chemistry field, we have paid particular attention to the N₂ and O₂ broadening.     

Nuclear quadrupole coupling in chloroform and calibration of ab initio calculations

The complex hyperfine structures in the J = 1 ← 0, and J = 2 ← 1 ground state rotational transitions of ³⁵Cl₃CH and ³⁵Cl₂³⁷ClCH were resolved and measured at conditions of supersonic expansion. Accurate spectroscopic constants for the two isotopomers have been derived from global fits of the hyperfine structure together with hyperfine-free high-J millimetre wave data. The complete inertial and principal quadrupole tensors of the chlorine nuclei have been determined, and the symmetric top treatment for ³⁵Cl₃CH and the asymmetric top treatment for ³⁵Cl₂³⁷ClCH yield identical results for the principal tensor components of the ³⁵Cl nucleus. The availability of precise experimental splitting constants for many molecules allows benchmarking of ab initio field gradient calculations, and it is found that for the chlorine nucleus optimum predictive performance for molecules of moderate size is obtained at the B3LYP/aug-cc-pVDZ level by using a scaling factor of 1.0619(23).     

Experimental and theoretical investigation on pressure-broadening and pressure-shifting of the 22.2 GHz line of water

Since water is a fundamental component of the atmosphere and it is well established that the accuracy of collisional broadening parameters has a crucial influence on reduction of remote sensing data, we decided to investigate the self-, N₂- and O₂-broadening parameters of the J=6_1,6←5_2,3 (22.2 GHz) rotational transition of water in the temperature range 296-338 K. Due to the relevance of this water line, this investigation should be considered of particular interest in monitoring the Earth's atmosphere, and therefore a particular effort has been made in order to reduce instrumental as well as systematic errors. Experimental determinations have also been supported by theoretical calculations.     

A Fabry-Perót type resonator tunable below 2 GHz for use in time domain rotational spectroscopy: Application to the measurement of the radio frequency spectra of bromobenzene and iodobenzene

Two aluminum mirrors with radii of 203.2 mm and radii of curvature also of 203.2 mm have been used to construct a tunable Fabry-Perót type resonator with Q values of ∼200 at frequencies as low as 500 MHz. The resonator has been incorporated into a pulsed nozzle, Fourier transform, Balle-Flygare spectrometer typically used for recording pure rotational spectra in the microwave region. The resonator design allows the instrument to access the radio frequency region (?3 GHz) of the electromagnetic spectrum. The spectrometer is of use in (i) recording low J transitions of large asymmetric molecules where the spectra are often greatly simplified compared to higher frequency regions; (ii) measuring hyperfine constants for heavy molecules with higher accuracy than may be obtained at higher frequencies where hyperfine structure may not be resolvable; and (iii) provides further synchronicity between laboratory based measurements and radio astronomy in the 30 cm region. The resonators use is illustrated by recording the rotational spectra of bromobenzene and iodobenzene. The lowest ΔJ = +1 transition for iodobenzene has been observed at 1130.5292(10) MHz.     

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.     

Spectral line parameters in the (3 ← 0) overtone band of the HI molecule and line-mixing in the band head

The linestrengths, self-pressure broadening and shifting coefficients have been measured for P₃ (10)- R₃ (12) lines in the second overtone band of hydrogen iodide. A dipole moment function in terms of the reduced nuclear displacement x = (R − R_e)/R_e is obtained using rotationless dipole matrix elements determined by the Herman-Wallis analysis of the (1, 2, 3 ← 0) HI bands: μ (x) = 0.4471(5) − 0.0770(2)x + 0.547(3)x² − 1.93(2)x³, in a full agreement with the function proposed previously [J. Mol. Spectrosc. 223 (2004) 67]. A close match is demonstrated of the results of most recent relativistic calculations [Phys. Chem. Chem. Phys. 6 (2004) 3779] with the spectroscopically derived electric dipole parameters for HI. Line-mixing in the band head is observed, the self-pressure shifting and broadening coefficients for the (3 ← 0) band lines are determined.