Xe-broadening coefficients of 12CH3D: a test of theoretical line shapes

We present the Xe-broadening coefficients for six lines belonging to the ν₃ band of ¹²CH₃D measured at room temperature with a diode-laser spectrometer. The collisional widths are obtained from least-squares fitting of each absorption line with theoretical line shapes. We used the well-known Voigt profile, the soft and hard collision models considering the collisional narrowing and also line shapes taking into account the speed dependence of the collisional cross-section. The results derived by these different models are compared with each other and with theoretical broadening coefficients. The calculations are based on a semiclassical impact formalism that includes the atom–atom Lennard–Jones potential for CH₃D–Xe interactions in which CH₃D is considered as a linear molecule.     

Collisional parameters of H2O lines: Velocity effects on the line-shape

This paper is devoted to the effects of velocity on the shapes of six R(J) lines of the ν₃ band of water vapor diluted in N₂. The experiments have been made at room temperature for total pressures between 0.1 and 1.2 atm using a tunable infrared laser frequency difference spectrometer. These measurements, which study broad and narrow lines of low and high J values, are first analyzed using the Voigt and the hard collision (HC) model. It is shown that both lead to unsatisfactory results, the Voigt profile being unable to account for the line narrowing whereas the friction (narrowing) parameter deduced using the HC approach has an unphysical dependence on pressure. Furthermore, at elevated pressure where Dicke narrowing and Doppler effects are negligible, deviations between experimental and fitted profiles are still observed, indicating inhomogeneous effects due to the speed dependence of collisional parameters. In order to go further, an approach based on the kinetic impact equation accounting for both the Dicke narrowing and the speed dependence has been applied. It uses velocity-dependent broadening and shifting coefficients calculated with a semi-classical approach and two parameters. The latter, which govern the memory functions of the modulus and orientation of the H₂O velocity are considered as free parameters and determined from experiments. The results show that all profiles, regardless of pressure and of the transition, can be correctly modeled using a single set of memory parameters. This demonstrates the consistency of the approach, which is then used to analyze the different regimes that monitor velocity effects on the line profile.     

Diode-laser spectroscopy: Temperature dependence of R (0) line in the ν4 band of CH4 perturbed by N2 and O2

In this paper, we present a line profile study of the R (0) line in the ν₄ band of methane diluted in nitrogen and oxygen, from room temperature to 153 K. The measurements were performed over a total pressure range from 14 to 128 mbar. The collisional broadening and narrowing (Dicke effect) coefficients are derived from a fit of the experimental spectra by using the soft and hard collision models, taking into account the Dicke effect. For higher pressures, we have fitted the data with a model taking into account simultaneously the Dicke narrowing and the speed dependence effect. Finally, we have deduced the parameter n of the temperature dependence (inverse power law) of the broadening coefficients for the CH₄-N₂ and CH₄-O₂ gas mixtures.     

H2-broadening,shifting and mixing coefficients of the doublets in the ν2 and ν4 bands of PH3 at room temperature

The broadening, shifting and mixing coefficients of the doublet spectral lines in the ν₂ and ν₄ bands of PH₃ perturbed by H₂ have been determined at room temperature. Indeed, the collisional spectroscopic parameters: intensities, line widths, line shifts and line mixing parameters, are all grouped together in the collisional relaxation matrix. To analyse the collisional process and physical effects on spectra of phosphine (PH₃), we have used the measurements carried out using a tunable diode-laser spectrometer in the ν₂ and ν₄ bands of PH₃ perturbed by hydrogen (H₂) at room temperature. The recorded spectra are fitted by the Voigt profile and the speed-dependent uncorrelated hard collision model of Rautian and Sobelman. These profiles are developed in the studies of isolated lines and are modified to account for the line mixing effects in the overlapping lines. The line widths, line shifts and line mixing parameters are given for six A₁ and A₂ doublet lines with quantum numbers K = 3n,?(n = 1,?2, …) and overlapped by collisional broadening at pressures of less than 50 mbar.     

Narrowing and Broadening Parameters for H2O Lines in the ν2 Band Perturbed by Nitrogen from Fourier Transform and Tunable Diode Laser Spectroscopy

Collision effects on water vapor line profiles perturbed by nitrogen at room temperature have been studied by Fourier transform and tunable diode laser spectroscopy. Narrowing effect due to molecular confinement (Dicke effect) has been observed for P and Q branch lines of the ν₂ band of H₂O with Fourier transform spectrometer. Narrowing and broadening parameters have been determined using the soft and hard collision models. A more precise study on three R-branch lines with a frequency stabilized diode laser spectrometer allows to perform the comparison between the two collision models at low pressure and to analyze the different narrowing effects when the pressure increases taking into account the molecular confinement and the absorber speed dependent effects.     

Evidence for collisional narrowing in the infrared laser Stark spectrum of CH3CN

The infrared laser Stark lineshape of the Jkm = 211 ← 111 transition in the ν₄ band of CH₃CN was recorded under computer control at several pressures. Analysis of the lineshapes by means of the usual Voigt profile gives a plot of collision broadening vs pressure that shows marked curvature in the low-pressure region. In addition, extrapolation to zero pressure of the best straight line through the high-pressure points gives a negative intercept. By choosing an appropriate narrowing parameter in either of the limiting soft-collision or hard-collision models of collisional narrowing, it is possible to obtain plots of collision broadening vs pressure that are linear and have acceptable intercepts. The pressure broadening and collisional narrowing parameters derived are 69.4 ± 0.7 and 17.2 ± 1.7 MHz/Torr, respectively, for the soft-collision model and 68.6 ± 0.7 and 11.5 ± 1.2 MHz/Torr, respectively, for the hard-collision model.     

Classical trajectory calculations for state-resolved Penning ionisation reactions of polycyclic aromatic hydrocarbon C10H8 in collision with He*(23S)

ABSTRACT

The reaction dynamics of Penning ionisation of a polycyclic aromatic hydrocarbon (PAH), naphthalene C₁₀H₈, in collision with the metastable He*(2³S) atom is studied by classical trajectory calculations using an approximate interaction potential energy surface between He* and the molecule, which is constructed based on ab initio calculations for the isovalent Li?+?C₁₀H₈ system. The ionisation width (rate) around the molecular surface are obtained from overlap integrals of the He 1s orbital and the molecular orbital. The calculated collision energy dependences of partial Penning ionisation cross sections (CEDPICS) in the range 50–500?meV at 300?K have reproduced the experimental results semi-quantitatively. The opacity functions, which represent the reaction probability with respect to the impact parameter b, are discussed in connection with collision energy, interaction with He* and the exterior electron density of molecular orbitals. They indicate that the collisional ionisations of C₁₀H₈ can be classified into three types: π electron ionisations with negative collision energy dependences which are predominantly determined by attractive interaction with He*; σ orbitals ionisations of the hardcore type; σ orbital ionisations which reflect interaction potentials around CH bonds. The critical impact parameters b_c become larger with increasing collision energy due to the centrifugal barrier.     

Self-broadening coefficients in the ν4 band of CH4 by diode-laser spectroscopy

With a diode-laser spectrometer, we have measured self-broadening coefficients of 42 lines of the P-, Q- and R-branches in the ν₄ fundamental band of CH₄ at room temperature, with J values ranging between 1 and 12. For the determination of self-broadening parameters, we have fitted to the experimental lineshape two theoretical line profiles: the Voigt profile taking into account Doppler and collisional broadenings, and the hard collision model developed by Rautian and Sobel’man incorporating Dicke narrowing.     

The absorption line profiles of H2O near 1.39 μm in binary mixtures with N2, O2, and H2 at low pressures

The absorption line profiles of water vapor in binary mixtures with diatomic molecules H₂, N₂, and O₂ have been recorded on a diode laser spectrometer. The profiles of several lines of the 101 band have been studied near 1.39 μm with a spectral resolution of 3 × 10^?4 cm^?1. The pressure of the binary mixtures was varied from 0 to 200 Torr. The experimental data obtained have been used to test the Voigt, Rautian-Sobel’man, and Galatry theoretical models of a spectral line profile. The coefficients of collisional narrowing have been determined from the results of the fitting.     

N2-broadening coefficients in the ν4 band of CH4 at room temperature

Using a diode laser spectrometer, we have studied with a great accuracy the N₂-broadening coefficients in the ν₄ band of methane. The experiments were performed at room temperature for lines in the P- and R-branches. We have measured 39 lines in the spectral range 1237–1373 cm⁻¹ with J values between 1 and 12. Each line under study was recorded at four different nitrogen pressures, ranging from 20 to 91 mbar. The collisional half-widths were obtained by fitting individually a theoretical profile on the experimental profile of each line at each N₂-pressure. We fitted the usual Voigt profile, but also the Rautian and Galatry lineshape models which take into account the collisional narrowing due to the molecular confinement (Dicke effect). The Rautian and Galatry fits are always better adjusted on the experimental profiles. For some lines, when the overlapping could not be disregarded, a fit of the blended profiles was performed using the same lineshape models. The collisional broadening coefficients obtained with Galatry and Rautian models are nearly equal and always higher than those derived from Voigt profile. Finally, we compare our results with previous determinations realized for several absorption bands.     

Narrowing and broadening parameters for H2O lines perturbed by helium,argon and xenon in the 1170–1440 cm−1 spectral range

Collision effects on water vapor at low concentration in a mixture with noble gases (helium, argon and xenon) have been studied by Fourier transform spectroscopy in the pressure range where line narrowing by dynamic confinement (Dicke effect) and collision broadening are observable, i.e. when the Voigt function cannot reproduce the observed profiles. Precise values of the broadening parameter have been obtained for the P and Q branches of the H₂O ν ₂ band taking into account molecular confinement (hard or soft collisions). The broadening parameter value derived from a Voigt profile for H₂O lines perturbed by helium is smaller by about 10% than values determined using the soft or hard collision model. For H₂O lines perturbed by argon or xenon this difference can reach more than 50% for the narrowest lines.     

The application of CARS for temperature measurements in high pressure combustion systems

The determination of accurate temperatures from CARS N₂ Q-branch spectra in premixed flames is discussed for pressures up to 40 bar. The influence of collisional line narrowing in the CARS spectra is modelled by a MEG fitting law. It takes into account collisions of N₂ with CO₂ and H₂O. The analysis of the CARS data showed that the non-resonant background has an increasing influence on temperature with increasing pressure. Little influence on the quality of the fit between theory and experiment was found. Since there is a danger of residual systematic temperature deviations, which cannot be identified from the quality of the fit, spontaneous rotational Raman scattering is employed as an independent measuring technique.     

Collisional narrowing of HF fundamental band spectral lines by neon and argon

Collisional narrowing is observed for high J transitions in the fundamental absorption band of HF in the presence of neon and argon buffer gases, with neon providing the most pronounced Doppler width reduction. Detailed line profiles are measured using a high-resolution tunable laser difference-frequency spectrometer in order to test various collisional lineshape models. The measured lineshapes and the pressure dependence of the widths are least-squares fit in the limits of strong and weak velocity-changing collisions. Though both limits qualitatively explain the data, the systematic discrepancies indicate that an intermediate collision model would be more appropriate. In the case of HF/argon collisions, the resulting line profiles have a slight, but definite, asymmetry, implying a correlation between the velocity- and state-changing collisions.     

High-resolution cavity ring-down spectroscopy measurements of blended H<Subscript>2</Subscript>O transitions

We probed four closely spaced rovibrational water vapor absorption transitions near =7100 cm^-1 using frequency-stabilized cavity ring-down spectroscopy. Room-temperature spectra were acquired for pure water vapor in the Doppler limit and for mixtures containing ≈6.6 μmol mol^-1 of water vapor in N₂ at total gas pressures ranging from 6.5 kPa to 53 kPa. By measuring Lamb dips for each transition, we demonstrated a resolution of 50 kHz and determined relative transition frequencies with an uncertainty <0.4 MHz over a 10 GHz range. Pressure-induced broadening, collisional narrowing coefficients of the component transitions and line areas were retrieved by fits of model line shapes to the measured spectra. Standard and advanced models were considered including those which incorporated the combined effects of collisional narrowing and speed-dependent line broadening and line shifting. By measuring water vapor concentration with a transfer standard hygrometer, we determined line intensities in terms of measured line areas with a combined relative uncertainty of 0.6%. PACS 33.20.-t; 33.70.Jg; 33.70.Fd; 42.62.Fi     

Effect of Supercollisions on Energy Transfer in Mixtures of Bath Gases and Laser Excited Complex Molecules

Intensities and decay rates of delayed luminescence (DL) initiated by a pulse of N₂ laser were employed to probe collisional relaxation of complex molecules (benzophenone, acetophenone) diluted with bath gases Ar, Kr, Xe, C₂H₄, SF₆, C₅H₁₂. It was shown that vibrational relaxation can be interpreted in terms of two consecutive processes: vibration-vibration (V-V) and vibration-translation (V-T). The results clearly demonstrated that fast component of DL can be used to study V-V energy transfer. It was found that at relatively small internal energy the collisional efficiences of V-V process had the values typical for molecular processes in which supercollisions contribute. The average energies transferred per collision, (ΔE), well correlated with predictions of the simple ergodic collision theory of intermolecular energy transfer.     

Intensities and shapes of H2O lines in the near-infrared by tunable diode laser spectroscopy

The integrated intensities, self- and air-broadening coefficients of thirteen transitions of H₂¹⁶O in the 11980–12260 cm^?1 region, belonging to the 2ν₁+ν₂+ν₃ band, were measured. Using a tunable diode laser system, spectra were recorded at room temperature for a wide range of pressure (2–15 Torr for pure H₂O and 50–760 Torr for H₂O in air). Line parameters were adjusted from experiments using three line-shape models: the Voigt profile (VP), the (hard collision) Rautian profile (RP) and the speed dependent Voigt profile (SDVP). The results show that the RP and SDVP are in better agreement with measurements than the VP and that they lead to larger values of the line parameters (about 5% for the line broadening, and 0.8% for the line intensity). Comparisons of the present results with HITRAN 2008 [Rothman et al., JQSRT 2009, 110:533-72] show that the HITRAN intensities of the studied lines are overestimated by about 9.4%, suggesting a more complete study of the H₂O line parameters in the considered region. The Dicke narrowing and speed dependence parameters deduced from this work are also presented and discussed, demonstrating the need for a more refined line-shape model.     

Three-body interaction-induced light scattering in krypton gas: a computer simulation of the spectral line shapes

The two-, three- and four-body effective collision induced scattering spectral line shapes are calculated for dense gaseous krypton using the pairwise additivity (PA) approximation and different polarizability models. These spectra and several interaction induced spectra calculated at various densities are compared with the experimental measurements of Barocchi et al. [1988, Europhys. Lett., 5, 607]. The potential effect on the spectrum is found to be weak. The results obtained with the Meinander et al. [1986, J. chem. Phys., 84, 3005] empirical polarizability model and molecular dynamics fit well the experimental two- and three-body spectral shapes. The irreducible contribution to the spectral shape is evaluated using the dipole induced dipole irreducible polarizability [buckingham, A. D., and Hands, I. D., 1991, Chem. Phys. Lett., 185, 544]. This contribution is found to be relatively weak for the anisotropic spectra in the frequency and density range studied, explaining the good agreement between the pairwise approximation calculations and the experimental data. The spectra radiated by the quasi-molecules Kr₂, Kr₃, and Kr₄ (the total spectrum within the PA approximation) are also simulated.     

Isotopic effects of the N(2D) + H2 → NH + H reaction: a quantum time-dependent wave packet investigation

Based on the potential energy surface reported by Li and co-workers (J. Comput. Chem. 34 1686–1696 (2013)), the dynamics calculations of N(²D)?+?H₂(v ₀?=?0, j ₀?=?0) reaction and its isotopic variants HD and D₂ are studied using time-dependent wave packet method in the collision energy range of 0.01–1.0?eV. Dynamics properties such as reaction probability, differential cross section, and integral cross section are studied at state-to-state level of theory. Present values are compared with available theoretical and experimental results. The results indicate that the integral cross sections of N(²D)?+?D₂ reaction are in general good agreement with the experimental data at collision energy below 0.15?eV. The rotational state-resolved integral cross sections of N(²D)?+?H₂/HD/D₂ reactions are compared with experimental values for the first time, with the obtained values being in good agreement with the experimental data.     

Spectral Intensity and Lineshape Measurements in the First Overtone Band of HF Using Tunable Diode Lasers

High-resolution absorption lineshapes for the P(3) and P(6) transitions of the first overtone (v = 2-0) band of HF at 296 K have been measured using a pair of distributed feedback diode lasers operating near 1.31 and 1.34 μm, respectively. Spectral line intensities and self-broadening parameters were determined by fitting the measured spectra with Voigt, Galatry, and Rautian lineshape models. Voigt profiles fit the low-pressure (<10 Torr) spectra of the P(3) transition reasonably well due to the relatively strong collisional broadening effect. Lineshape measurements of the P(6) transition (for pressures ranging from 5 to 60 Torr) show significant variation from the Voigt lineshape model due to velocity-changing collisions that effectively reduce the Doppler component of the spectral line. Lineshape models that include motional (Dicke) narrowing effects, Galatry (soft collision) and Rautian (hard collision) profiles yield significant improvements in the spectral lineshape fits compared with Voigt profiles. The collisional broadening coefficient (gamma) of the P(6) transition obtained from a Voigt fit is approximately 4% lower than those found with either Galatry or Rautian profile fits. The measured intensities and self-broadening coefficients are compared with values in the HITRAN database and previous measurements. Copyright 1999 Academic Press.     

Diode laser measurements of temperature-dependent collisional-narrowing and broadening parameters of Ar-perturbed H2O transitions at 1391.7 and 1397.8 nm

High-resolution absorption lineshapes of two H₂O transitions near 7185.60 and 7154.35 cm⁻¹ have been recorded in a heated static cell as a function of temperature (296-1100 K) and pressure (6-830 Torr) using two distributed-feedback diode lasers. The measured absorption spectra are least squares fit to both Voigt and Galatry profiles. Strong collisional-narrowing effects are observed in the Ar-broadened H₂O spectra at near-atmospheric pressure due to the relatively weak collisional broadening induced by Ar-H₂O collisions, while collisional narrowing is not significant for pure H₂O absorption lineshapes. Line strengths and self-broadening coefficients are inferred from the pure H₂O absorption spectra and compared with published data. Temperature dependences of the Ar-induced broadening, narrowing, and shift coefficients are determined using Galatry fits to the absorption data. The measured collisional-narrowing parameters have similar temperature dependence to the collisional-broadening coefficients.