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Information about molecular collisions is encoded in the shapes of collision-perturbed molecular resonances. This connection between molecular interactions and line shapes is most clearly seen in simple systems, such as the molecular hydrogen perturbed by a noble gas atom. We study the H2–Ar system by means of highly accurate absorption spectroscopy and ab initio calculations. On the one hand, we use the cavity-ring-down-spectroscopy technique to record the shapes of the S(1) 3-0 line of molecular hydrogen perturbed by argon. On the other hand, we simulate the shapes of this line using ab initio quantum-scattering calculations performed on our accurate H2–Ar potential energy surface (PES). In order to validate the PES and the methodology of quantum-scattering calculations separately from the model of velocity-changing collisions, we measured the spectra in experimental conditions in which the influence of the latter is relatively minor. In these conditions, our theoretical collision-perturbed line shapes reproduce the raw experimental spectra at the percent level. However, the collisional shift, δ0, differs from the experimental value by 20%. Compared to other line-shape parameters, collisional shift displays much higher sensitivity to various technical aspects of the computational methodology. We identify the contributors to this large error and find the inaccuracies of the PES to be the dominant factor. With regard to the quantum scattering methodology, we demonstrate that treating the centrifugal distortion in a simple, approximate manner is sufficient to obtain the percent-level accuracy of collisional spectra. [ABSTRACT FROM AUTHOR]

The CO2 molecule is of great interest for astrophysical studies since it can be found in a large variety of astrophysical media where it interacts with the dominant neutral species, such as He, H2, or H2O. The CO2–He collisional system was intensively studied over the last two decades. However, collisional data appear to be very sensitive to the potential energy surface (PES) quality. Thus, we provide, in this study, a new PES of the CO2–He van der Waals complex calculated with the coupled-cluster method and a complete basis set extrapolation in order to provide rotational rate coefficients that are as accurate as possible. The PES accuracy was tested through the calculations of bound state transition frequencies and pressure broadening coefficients that were compared to experimental data. An excellent agreement was globally found. Then, revised collisional data were provided for the 10–300 K temperature range. Rate coefficients were compared to previously computed ones and are found to be up to 50% greater than previously provided ones. These differences can induce non-negligible consequences for the modeling of CO2 abundance in astrophysical media. [ABSTRACT FROM AUTHOR]

In this study, two series of pressurized turbulent jet sooting flames at 1, 3, and 5 bar with either fixed jet velocity or fixed Reynolds number are simulated to study the pressure effects on soot formation and evolution. Through a radiation flamelet progress variable approach with a conditional soot subfilter probability density function (PDF) model to consider the turbulence–chemistry–soot interactions, quantitatively good agreements are achieved for soot volume fraction (SVF) predictions compared with the experimental data, regardless different turbulent intensities and residence times. SVF source terms are then discussed to show the pressure effects on nucleation, condensation, surface growth, and oxidation at different axial positions in these flames. It is found that surface growth and oxidation increase by about three orders of magnitude from 1 to 5 bar, while nucleation and condensation only increase within one order of magnitude. The stronger SVF scaling on pressure than measured data is found to be attributed to the inaccurate surface growth and oxidation scaling on pressure. Further analysis indicates that (i) the uncertainty of C2H2 prediction at elevated pressures is likely a major reason for the too strong surface growth scaling; and (ii) taking account of pressure effects in the conditional subfilter PDF modeling for turbulence–soot–chemistry interactions is likely a key to improve oxidation prediction. The results in this study open up the possibilities for improving future turbulent sooting flame modeling by improving C2H2 chemistry and turbulence–chemistry–soot modeling at elevated pressures. [ABSTRACT FROM AUTHOR]

We show how to effectively introduce a proper description of the velocity-changing collisions into the model of isolated molecular transition for the case of self- and Ar-perturbed H² .We demonstrate that the billiard-ball (BB) approximation of the H²-H² and H²-Ar potentials gives an accurate description of the velocity-changing collisions. The BB model results are compared with ab initio classical molecular dynamics simulations. It is shown that the BB model correctly reproduces not only the principal properties such as frequencies of velocity-changing collisions or collision kernels, but also other characteristics of H² and H²-Ar gas kinetics like rate of speed-changing collisions. Finally, we present line-shape measurement of the Q(1) line of the first overtone band of self-perturbed H² . We quantify the systematic errors of line-shape analysis caused by the use of oversimplified description of velocity-changing collisions. These conclusions will have significant impact on recent rapidly developing ultra-accurate metrology based on Doppler-limited spectroscopic measurements such as Doppler-width thermometry, atmosphere monitoring, Boltzmann constant determination, or transition position and intensity determination for fundamental studies. [ABSTRACT FROM AUTHOR]

Inelastic H2:He collisions are studied from the experimental and theoretical points of view between 22 and 180 K. State-to-state cross sections and rates are calculated at the converged close-coupling level employing recent potential energy surfaces (PES): The MR-PES [J. Chem. Phys. 100, 4336 (1994)], and the MMR-PES and BMP-PESs [J. Chem. Phys. 119, 3187 (2003)]. The fundamental rates k2→0 and k3→1 for H2:He collisions are assessed experimentally on the basis of a master equation describing the time evolution of rotational populations of H2 in the vibrational ground state. These populations are measured in the paraxial region of supersonic jets of H2+He mixtures by means of high-sensitivity and high spatial resolution Raman spectroscopy. Good agreement between theory and experiment is found for the k2→0 rate derived from the MR-PES, but not for the BMP-PES. For the k3→1 rate, which is about one-third to one-half of k2→0, the result is less conclusive. The experimental k3→1 rate is compatible within experimental error with the values calculated from both PESs. In spite of this uncertainty, the global consistence of experiment and theory in the framework of Boltzmann equation supports the MR-PES and MMR-PESs, and the set of gas-dynamic equations employed to describe the paraxial region of the jet at a molecular level. [ABSTRACT FROM AUTHOR]

Theory and experiment are combined in a novel approach aimed at establishing a set of two-body state-to-state rates for elementary processes ij→ℓm in low temperature N2:N2 collisions involving the rotational states i,j,ℓ,m. First, a set of 148 collision cross sections is calculated as a function of the collision energy at the converged close-coupled level via the MOLSCAT code, using a recent potential energy surface for N2–N2. Then, the corresponding rates for the range of 2≤=T≤=50 K are derived from the cross sections. The link between theory and experiment, aimed at assessing the calculated rates, is a master equation which accounts for the time evolution of rotational populations in a reference volume of gas in terms of the collision rates. In the experiment, the evolution of rotational populations is measured by Raman spectroscopy in a tiny reference volume (≈2×10-3 mm3) of N2 traveling along the axis of a supersonic jet. The calculated collisional rates are assessed experimentally in the range of 4≤=T≤=35 K by means of the master equation, and then are scaled by averaging over a large set of experimental data. The scaled rates account accurately for the evolution of the rotational populations measured in a wide range of conditions. Accuracy of 10% is estimated for the main scaled rates. [ABSTRACT FROM AUTHOR]

Inelastic collisions in natural H2 are studied from the experimental and theoretical points of view between 10 and 140 K. Rotational populations and number densities measured by Raman spectroscopy along supersonic expansions of H2 provide the link between experimental and theoretical rotranslational state-to-state rate coefficients of H2 in the vibrational ground state. These rates are calculated in the close- scattering approach with the MOLSCAT code employing a recent ab initio H2–H2 potential. The calculated rates are assessed by means of a master equation describing the time evolution of the experimental rotational populations. The feasibility for obtaining the rates on the sole basis of the experiment is discussed. The dominant processes j1j2→j1′j2′ in the investigated thermal range are found to be 21→01>30→12>31→11, proving the importance of double processes such as 30→12. Good agreement is found between theory and experiment, as well as with earlier ultrasonic measurements of relaxation times. A spectral representation is proposed in order to visualize quantitatively the collisional contributions in any nonequilibrium time evolving process. [ABSTRACT FROM AUTHOR]

We report an experimental determination of the k00→02 rate coefficient for inelastic H2:H2 collisions in the temperature range from 2 to 110 K based on Raman spectroscopy data in supersonic expansions of para-H2. For this purpose a more accurate method for inverting the master equation of rotational populations is presented. The procedure permits us to reduce the measured k00→02 rate coefficient to the corresponding σ00→02 cross section in the range of precollisional energy from 360 to 600 cm-1. Numerical calculations of σ00→02 carried out in the frame of the coupled channel method are also reported for different intermolecular potentials of H2. A good agreement is found between the experimental cross section and the numerical one derived from Diep and Johnson’s potential [J. Chem. Phys. 112, 4465 (2000)]. [ABSTRACT FROM AUTHOR]

In a previous paper [J. Chem. Phys. 116, 7544 (2002) (Paper I)] a model, based on the energy corrected sudden approximation, was proposed for the construction of the line-mixing relaxation matrix. It was successfully tested by comparisons with measured infrared spectra of ammonia–helium mixtures. The present paper extends this preliminary study by considering mixtures of NH[sub 3] with H[sub 2] and Ar. Measurements have been made at room temperature in the regions of the ν[sub 2] and ν[sub 1] bands for pressures up to several hundred atmospheres. As in Paper I, the relaxation operator is constructed, within the impact approximation, using the ECS approximation. The data required are dynamical factors (which can be predicted from the NH[sub 3]–X potential energy surface) and a scaling length (adjusted using line broadening data). Comparisons between measured and calculated absorptions demonstrate the quality of the model which satisfactory corrects for the large deviations with respect to the purely Lorentzian behavior. Line-mixing effects for NH[sub 3]–Ar and NH[sub 3]–H[sub 2] are qualitatively similar to those observed for NH[sub 3]–He but quantitative differences exist, particularly when intra- and interbranch couplings are considered. Finally, the proposed model leads to very satisfactory results in the wings of both the purely rotational and ν[sub 2] bands of NH[sub 3] diluted in H[sub 2], opening promising perspectives for the remote sensing study of planetary atmospheres. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Fully quantal scattering calculations are carried out for CO in argon using both the close coupling (CC) and coupled states (CS) methods. CC and CS cross sections σ(j→j[sup ′]) generally agree to within 15% or less with the exception of those corresponding to low Δj=|j[sup ′]-j| values at low j where differences may reach 50%. The discrepancy arises mostly from efficient collisions with large orbital angular momentum, where the rotation of the quantization axis can no longer be neglected. Then, the CC calculations were used to test a scaling procedure based on the energy corrected sudden (ECS) approximation: given a set of basic cross-section σ(j→0), is it possible to predict the entire σ[sup o](j→j[sup ′]) relaxation matrix? The ECS procedure yields reasonable agreement, on average, at the 13% level. However it fails at reproducing the Δj=1 cross sections in cases where the concept of a mean adiabaticity factor losses its physical meaning since the duration of the efficient collisions varies too much with the orbital angular momentum. On that basis, we have examined another question: the validity of an inversion procedure, based on the ECS scheme. Is it possible to determine the basic cross sections σ(j→0) starting from the knowledge of the easily measurable diagonal elements σ[sup o](j→j)? The ECS inverted basic rates agree with the CC ones to within about 20% up to j=15 and strongly diverge for higher j while the inversion leads to an overestimation of the mean duration of the efficient collisions. Then, using a high resolution Raman spectrometer, we recorded the Q-branch head of the fundamental band of CO in mixture with Ar at three temperatures, 87, 195, and 300 K, and total pressures up to 1.25 bar. Line-mixing effects in experimental Raman profiles are compared with CC theoretical predictions. Finally the close coupling results are also used to predict rotational relaxation times measured in free jets. © 2003 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We present an experimental determination of state-to-state rotational-translational (RT) rate constants of N[SUB2]:He collisions in the vibrational ground state as a function of temperature in the range 3

We present measurements of Raman linewidths in the fundamental Q branch of CO for mixtures with Ar at temperatures of 77, 195, and 300 K, recorded using an inverse Raman spectrometer. Starting from a recent ab initio potential energy surface, theoretical values of Ar broadening coefficients for CO infrared and Raman lines (isotropic and anisotropic components) at temperatures in the range 77 to 1100 K are calculated via quantum-mechanical methods. The relative merits of the close coupling theoretical results over the coupled states results are underlined. Finally, a comparison of the calculated pressure broadening coefficients is made with the present experimental data as well as with recently available infrared data. There is general agreement between the calculated and measured values of the broadenings for all the temperatures probed. We conclude that the temperature dependence of the infrared and Raman broadening coefficients have been correctly determined theoretically and may be used to test a common temperature scaling law. [ABSTRACT FROM AUTHOR]

Line mixing effects have been studied in the ν[sub 2] and ν[sub 1] parallel bands of NH[sub 3] perturbed by He at room temperature. Experiments have been made with a Fourier transform spectrometer covering a wide range of total pressures up to about 400 atm. Analysis of the spectra demonstrates, for the first time, that the spectral shapes of entire ammonia bands can be significantly influenced by line mixing. A theoretical approach based on the energy corrected sudden approximation (ECS) is used to predict and analyze these effects. The model parameters include dynamical factors directly computed from an NH[sub 3]–He potential energy surface and a scaling length which has been determined from a fit of line-broadening data. Comparisons with measurements show that the ECS model leads to surprisingly satisfactory predictions when considering the large spacing between rotational levels. The large effects of line mixing within the Q branches and in the far wing of the absorption bands are analyzed. It is shown that purely Lorentzian calculations can lead to underestimation of the Q branch peak by a factor of up to 4, whereas the overestimation of absorption in the band wing reaches one order of magnitude. On the contrary, the proposed ECS approach leads to much better results and accounts for most of the transfers of intensity among the various spectral components. It is used for the analysis of the shape of Q branches, P and R manifolds and line wings. Remaining discrepancies are discussed in terms of the model approximations and the improper dependence of the basis dynamical factors on quantum numbers induced by uncertainties on the potential energy surface used. © 2002 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The fundamental isotropic Raman Q-branch of CO has been recorded using Raman loss spectroscopy for mixtures with helium at low temperatures (77–195 K). Accurate close coupling calculations of both diagonal and off diagonal (line coupling) cross sections have been performed starting from one of the best available potential energy surfaces [T. G. A. Heijmen, R. Moszynski, P. E. S. Wormer, and Ad van der Avoird, J. Chem. Phys. 107, 9921 (1997)]. Predictions are in good agreement with Q-branch Raman data. These results, which corroborate previous analysis based on IR absorption data, are a further test of the adequacy of the close coupling formalism for the prediction of line shapes in a rather wide range of physical situations (pressure, temperature, type of spectroscopy...), when an accurate potential exists. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We present measurements of the shifts and widths of the rovibrational lines of the fundamental band of CO highly diluted in He and Ar at 296 K. The shifts are decomposed into parts odd and even in the line number, m. These are then compared with close coupled calculations carried out with the best known interaction potentials. There is general agreement between the calculated and measured values of the broadening and shifting. Furthermore, the results illustrate that the decomposition of the shifts into parts, odd and even in m, is a powerful tool for separating out the relative contributions of the isotropic and anisotropic part of the interaction to the shifts and which part needs to be corrected if there is a discrepancy. Thus, shift measurements can be added to the list of experiments that may be used to determine reliable interaction potentials. The results also show, given a potential, that close coupled calculations are accurate and could be used to confirm or establish empirical models of the temperature dependence of the broadening or shifting, etc. Such modeling is important at atmospheric physics. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Line coupling induced by collisions leads to drastic modifications of the spectral profile of the 0003–0000 of CO2 pressurized by helium. Calculation of these modifications have been performed by using two recent energy corrected sudden (ECS) formalisms. The two formulations lead to theoretical predictions rather similar and in good agreement with the available data over extended ranges of frequency and perturber pressure. It has been shown that a simultaneous fit of the pressure broadened linewidths and the near wing profile allows a more accurate determination of the basic ECS parameters. For that purpose, it has been necessary to extend the measurement of the broadened widths to high J values (up to J≊90). [ABSTRACT FROM AUTHOR]

The shape of the 00°3–00°0 CO2 band in helium has been investigated at room temperature over an extended range of perturber pressures (0–140 atm). Various and strong deviations from an additive superposition of Lorentzian lines have been observed, due to important line mixing effects enhanced by the specific structure of the R branch in this band. [ABSTRACT FROM AUTHOR]

In paper I of this series, important deviations from an additive superposition of Lorentzian profiles were experimentally evidenced in the 00°3–00°0 band of CO2 in He. All the observed deviations are explained by the collision-induced line mixing effects which schematically transfer intensity from the wing of the band to its central part. The IOS approximation has been found to be insufficient while, the ECS approximation leads to theoretical predictions in good agreement with the experimental data over extended ranges of frequency and perturber pressure. However it must be emphasized that it has been necessary to resort to the method in current use for the determination of the fundamental rates, an ad hoc adjustement starting from the observed linewidths. [ABSTRACT FROM AUTHOR]

Here we present the first line-by-line measurements of interference parameters Y0k describing line-mixing effects in the weak overlapping regime for He-broadened CO lines in the 0–1 and 0–2 bands at 296 K. A detailed analysis of the line shape at intermediate perturber pressures (up to about 10 atm) has been performed, starting from previous theoretical calculations, which has demonstrated the possibility of an individual measurement of Yk parameters. The method is based on the existence of a component of the line shift, quadratic with the perturber pressure (density) and proportional to Y0k. Comparison of our measurements with results predicted from coupled-states calculations shows good overall agreement. Linear pressure shifts have also been simultaneously measured. The uncertainty on the data is important since linear shifts are very small; however, some features can be considered as significant although we have no clear understanding of them. Possible explanations are discussed. [ABSTRACT FROM AUTHOR]

Self-broadened and N2, Ar, He-broadened halfwidth and pressure shift coefficients of the rotational transitions in the 0003–0000 band of 12C16O2 have been measured from laboratory absorption recorded at room temperature with a Fourier transform spectrometer. Comparison is made with the results of a theoretical calculation based on a semiclassical model. Good agreement is obtained for all the IR vibrational bands for which data are available. It has been shown that the shifts mainly originate from vibrational dephasing. Infrared line shifts have been compared with results obtained from stimulated Raman spectroscopy and we show that they are not consistent. A number of possible explanations have been discussed to account for this discrepancy. [ABSTRACT FROM AUTHOR]

Investigates the accuracy of energy-corrected sudden (ECS) formalism for line shape calculations. Estimation of the coupled states of carbon dioxide-argon collisions; Observation on the ECS linewidths; Convergence of the coupled-state calculations.