Experimental microwave collision diameters in the rotational spectrum of H2CO

Collision diameters for some select transitions in the rotational spectrum of H₂CO have been determined using pressure broadening of the spectral lines. Transitions of the type ΔJ = 0, K_?1 = 1, and ΔK₊₁ = 1 with 1 ≤ J ≤ 5 were investigated for both self-broadening and foreign gas broadening (He and H₂) of the spectral lines. Pressure ranges from 0.001 Torr to 0.1 Torr were explored in obtaining the line width parameters Δν_p for each transition. Collision diameters were found to be very nearly constant (14 Å) over the J states studied for H₂COH₂CO interaction, 2.5–5.8 Å for H₂COH₂ interaction and 2.7–3.5 Å for H₂COHe interaction.     

Broadening of vibrational-rotational lines of the H2S molecule by pressure of monatomic gases

Optimal sets of parameters for a model intermolecular potential that provide the best reproduction of broadening coefficients γ for the absorption lines in the ν₂ band of the H₂S molecule are determined for systems H₂S-A (A = He, Ne, Ar, Kr, and Xe). For H₂S-He, the potential is obtained with the temperature dependence of coefficients γ taken into account for two rotational absorption lines 1₁₀ ← 1₀₁ and 2₁₁ ← 2₀₂. With the potentials obtained, the coefficients γ are calculated for the ν₁ and ν₃ bands and compared with the available experimental data. There are significant discrepancies between the calculated and experimental values of γ.     

Self-Broadening and Carbon-Dioxide Broadening of Lines of the H<Subscript>2</Subscript>S Molecule

Carbon-dioxide-broadening coefficients and self-broadening coefficients of lines of the main isotopic modification of Н₂S are estimated on the basis of literature data. The J′-dependences of the above line-profile parameters of the hydrogen-sulfide molecule are examined. In the case of CO₂ broadening, the half-widths of lines are calculated by a semiempirical method based on a parametric modification of the impact semiclassical model; the model parameters were determined from the fit to experimental data.     

Measurements and calculations of self-broadening coefficients of lines belonging to the v2 band of H216O

The self-broadening coefficients of 150 lines belonging to the v₂ band of H₂¹⁶O between 1770 and 2250 cm^-1 have been measured using Fourier transform spectra (resolution ≈ 0.005 cm^-1). The four different methods which have been used to deduce the self-broadening coefficients from experiment are described in detail. The estimated average uncertainty is about 15% and varies from 7 to 30%, depending on the method used and on the line involved. Two theoretical calculations, one based on the Anderson-Tsao-Curnutte method and the other on the recent method proposed by Davies, have been performed, retaining only the dipole-dipole interaction. For some lines of the v₂ band and for some pure rotation lines, calculations based on other formalisms have also been performed. For all of these calculations, we have used accurate spectroscopic data: precise energy levels, realistic wavefunctions, and a complete dipole-moment operator expansion in order to compute the transition probabilities. As compared to the previously calculated values of the pioneering work of Benedict and Kaplan, where the Anderson-Tsao-Curnutte method was used, our calculations show improvements by about 14% in the agreement between measured and calculated self-broadening coefficients.     

Largeurs des raies spectrales de CO autoperturbe et perturbe par N2, O2, H2, HCI,NO et CO2

Linewidths of CO self-broadening and broadened by N₂, O₂, H₂, HCI, NO, and CO₂ have been calculated using different contributions in the intermolecular dispersion potential.The quadrupole moment of some perturbers has been determined by comparison between calculated and observed linewidths. The values obtained for the quadrupole moments may depend on the dispersion potential, especially when it is low (as is the case for N₂, O₂ and H₂). For CO-CO and CO-NO, the electrostatic interactions including the octupole moment yield good results for the linewidths for high |m|-values.     

Broadening and collisional interference of lines in the IR spectra of ammonia: Self-broadening in the ν<Subscript>1</Subscript> band

The relaxation parameters of the lines of the P, Q, and R branches of the ν₁ ammonia ν₁ band are calculated in the case of self-broadening. In the case of doublets, the effects of collisional interference of the doublet components have been taken into account. It is shown that the cross-relaxation parameters of the components can reach ~60% of the values of the self-broadening coefficients, which gives rise to the narrowing of the components and indicates that the isolated line approximation is inapplicable. Comparison with experimental data is made. Good agreement for self-broadening coefficients is obtained. In the case of the self-shift coefficients, discrepancies are considerable in both magnitude and sign, and it is impossible to elucidate their reasons without invoking additional experimental data.     

Broadening and collisional interference of lines in the ir spectra of ammonia: Self-broadening in the ν<Subscript>2</Subscript> band

The relaxation parameters of lines of the P, Q, and R branches of the ammonia ν₂ band are calculated in the case of self-broadening with the effects of collisional interference of doublet components taken into account. It is shown that the cross-relaxation parameters do not exceed, as a rule, several percent of the values of the self-broadening coefficients and, consequently, the isolated line approximation is applicable in a wide pressure range. The calculated results are compared with experimental data.     

Temperature dependence of the self-broadening coefficients of ethane

Using a diode-laser spectrometer, self-broadening coefficients have been measured at three temperatures (246.2, 226.2 and 150.2 K) for 11 spectral lines in the ν₉ fundamental band of ¹²C₂H₆. The collisional widths have been obtained by fitting each experimental absorption profile with a Rautian model. The temperature dependence exponent n was also determined for each line, and found to be constant within experimental uncertainties. The mean value is equal to n = 0.676.     

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.     

A multispectrum analysis of the ν2 band of HCN: Part II. Theoretical calculations of self-broadening, self-induced shifts, and their temperature dependences

A semiclassical theory based upon the Robert-Bonamy formalism has been developed to explain the experimental measurements of self-broadening, self-induced pressure shift coefficients in the ν₁,ν₂, 2ν₂ bands of H¹²C¹⁴N and the 2ν₁ band of H¹³C¹⁴N, as well as the temperature dependences of these parameters with special emphasis on the ν₂ band. Our calculations include only electrostatic interactions and neglect the vibrational dependence of the isotropic part of the intermolecular potential, which probably has a weak contribution to the HCN self-shifts for the bands investigated in this study. The agreement between theory and measurements is good in the cases of self-broadening coefficients and their variation with temperature, as well as the self-shift coefficients determined at room temperature. However, the observed temperature dependence of self-shift coefficients in the ν₂ band is different from that derived theoretically.     

Contribution des moments octupolaire et hexadecapolaire a l'elargissement des raies spectrales de molecules linearaires

Expressions for linewidths due to hexadecapole-dipole, hexadecapole-quadrupole, hexadecapole-octupole, and hexadecapole-hexadecapole interactions have been determined from the Anderson-Tsao-Curnutte theory. We have shown—for linewidths of CO₂ with self-broadening and broadened by N₂, as well as for linewidths of CO with self-broadening and broadened by N₂, O₂, H₂, and CO₂—that allowance for octupolar and hexadecapolar mements yields improved agreement with experimental data for high |m|-values.     

Pressure-broadened linewidths of hydrogen sulfide

Self-broadened and foreign-gas (N₂ and O₂) broadened linewidths of H₂S at 300°K have been calculated using the Anderson-Tsao-Curnutte theory of line broadening for a wide range of quantum numbers J and K_a, in both type A and type B bands. Computed values for self-broadened linewidths are in good agreement with the experimental results of Helminger and De Lucia. Air-broadened linewidths of H₂S at 200°K have also been calculated, so that the temperature dependence can be estimated.     

Linewidth and intensity measurements of SO2 lines at 94 GHz with self-broadening and broadening by H2O and N2

In the frequency range between 91.5 and 95.5 GHz, three rotational lines of the ³²S¹⁶O₂ and two rotational lines of the ³⁴S¹⁶O₂ molecules in the fundamental vibrational state, and also two lines of the ³²S¹⁶O₂ molecule in the v₂ vibrational state, have been investigated. Center frequencies and absolute absorptions have been measured and compared with theoretical values. Furthermore, the self-broadening and broadening by H₂O and N₂ of the transition 23(6,18)–24(5,19) with the line center at 94.064 GHz have been investigated. The following linewidth parameters were found: SO₂-SO₂, 18.2±0.3 MHz/torr; SO₂-N₂, 3.8±0.1 MHz/torr; SO₂-H₂O, 15.2±0.2 MHz/torr. The bridge spectrometer and the measuring method used are also described.     

The N2-broadened water vapor absorption line shape and infrared continuum absorption—II. Implementation of the line shape

The total line shape model of the previous paper is tested using a set of experimental room temperature H₂O continuum measurements of high quality. Parameters of the far wing component of the total line shape are determined from near band experimental data. Grating spectrometer measurements from 300 to 650 cm^?1 are used to determine unknown far wing parameters of the pure rotational band of H₂O. CO and HF laser measurements taken in the 5 and 3 μm regions are used to determine the far wing parameters of the ν₂ and ν₁, ν₃ fundamental bands, respectively.The total line shape model is applied to the 10 and 4 μm transmission windows with encouraging success. A significant increase in the self-broadening ability of H₂O over N₂ is predicted in the far wing. This procedure allows the proper modeling of the absorption coefficient vs H₂O partial pressure dependence in all window regions. A negative temperature is predicted by the model in the continuum. The observed rate of the temperature decrease is not predicted by the model; however, this limitation is related to the approximations made on the interaction potentials and the perturbation expansion of the Hamiltonians. Although the total line shape has limitations, it does demonstrate the importance of considering far wings of absorption lines in continuum absorption.     

Pressure broadened line widths of BrCN in the microwave region

The line widths of cyanogen bromide (BrCN) have been measured at room temperature (305 K) by using a double modulation microwave spectrograph. The self-broadening of two quadrupole hyperfine lines of the transition J = 3 → 4 has been measured. The foreign gas broadening by OCS, CO₂, N₂, CH₃CN, CH₃I, HCHO and CH₃CHO molecules has been measured only for the intense line at 32·957 GHz. These measured line widths have been compared with the calculated line widths using Anderson [6] as well as Murphy and Boggs [8] theories of pressure broadening.     

Line shift and mixing in the ν4 and 2ν2 band of NH3 perturbed by H2 and Ar

Pressure induced line shift and line mixing parameters have been measured for 66 rovibrational lines in the ν₄ band and for 10 lines in the 2ν₂ band of NH₃ perturbed by H₂ and Ar at room temperature (T = 296 K). These lines with J values ranging from 2 to 10 are located in the spectral range 1450-1600 cm⁻¹. Experiments were made with a high-resolution Fourier transform spectrometer. The line shifts and line mixing parameters have been derived from the non-linear least-square multi-pressure fitting technique. The shift coefficients are compared with those calculated from the Robert-Bonamy formalism (RB). The results are generally in satisfactory agreement with the experimental data.     

Ab initio potential energy curves and vibrational levels for the c, l, and i states of the hydrogen molecule

Potential energy curves for the hydrogen molecule in the c³Π_u, I¹Π_g, and i³Π_g state have been calculated in the Born-Oppenheimer approximation. Highly flexible wavefunctions have been used, and for each state the calculations have been carried out for 40 different internuclear distances in the region 1 ≤ R ≤ 12 a.u. For the Π_g states the wavefunctions are known to change their character around R = 5 a.u. The effect of this change on various components of the energy has been analyzed. The vibrational Schrödinger equation for all states has been solved for H₂, HD, and D₂. For H₂ the resulting energies are compared with the experimental values and it is shown that the adiabatic effects are likely to be responsible for the existing discrepancy between the theoretical and experimental values.     

Self-broadening, self-shift and self-mixing in the ν2, 2ν2 and ν4 bands of NH3

Using Fourier-transform spectra (Bruker IFS 120 HR, resolution ≈0.004 cm⁻¹) of NH₃ in nine branches of the ν₂, 2ν₂ and ν₄ bands, self-broadening and self-shift as well as self-mixing coefficients have been determined at room temperature (T=295 K) for more than 350 rovibrational lines located in the spectral range 1000–1800 cm⁻¹. A non-linear least-squares multispectrum fitting procedure, including line mixing effects, has been used to retrieve successively the line parameters from 11 experimental spectra recorded at different pressures of pure NH₃. The accuracies of self-broadening coefficients are estimated to be better than 2% for most lines. The mean accuracies of line-mixing and line-shift data are estimated to be about 15% and 25%, respectively. The results are compared with previous measurements and with values calculated using a semiclassical model based upon the Robert–Bonamy formalism that reproduces rather well the systematic experimental J and K quantum number dependencies of the self-broadening coefficients.The results concerning line mixing demonstrate a large amount of coupling between the symmetric and asymmetric components of inversion doublets mainly in the ν₄ band. The line mixing parameters are both positive and negative. More than two thirds of the lines studied here have a positive shift coefficient. However, for most of them the shift coefficients are negative in the 2ν₂ band. They are positive for the R branch of the ν₂ band and for the ^PR and ^RP branches of the ν₄ band. For the other branches they are both positive and negative. Some components of inversion doublets illustrate a correlation between line mixing and shift phenomena demonstrated by a quadratic pressure dependence of line position.     

Improved potential energy curve and vibrational energies for the electronic ground state of the hydrogen molecule

The potential energy curve for the electronic ground state of the hydrogen molecule has been recomputed for intermediate and large internuclear separations. for 2.4 ≤ R ≤ 8.0a.u. the previous potential energy curve has been improved. The largest improvement amounts to 5.5 cm^?1, and was obtained in the vicinity of R = 4.4a.u.. Using the new potential energy curve, and the adiabatic and relativistic corrections, the vibrational and rotational energy levels have been calculated for H₂, HD, and D₂. The deviations of the calculated energy levels G(v) of H₂ and D₂ from the observed values follow very closely the nonadiabatic corrections resulting from the Van Vleck formula.     

Diode laser spectroscopy of H2O and CO2 in the 1.877-μm region for the in situ monitoring of the Martian atmosphere

A diode laser spectrometer was used in the laboratory to study H₂O and CO₂ line intensities and self-broadening coefficients around 1.877 μm. The spectral region ranging from 5327 cm^-1 to 5329 cm^-1, which is suitable for the in situ sensing of water vapor and carbon dioxide in the Martian atmosphere, was studied using a distributed feedback GaInSb diode laser from Nanoplus GmbH. We have studied one line from the (011)←(000)band of H₂O and two lines from the (01¹2)_I←(000) band of CO₂. The results of intensity and self-broadening measurements are compared to available databases, ab initio calculations and previous experimental determinations. Finally, we discuss the current development of the tunable diode laser absorption spectrometer instrument, a laser diode sensor devoted to the in situ measurement of H₂O and CO₂ in the Martian atmosphere. PACS 07.57.Ty; 07.87.+v