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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]

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

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]

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]