<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mi mathvariant="normal">H</mml:mi><mml:mn>2</mml:mn></mml:msub></mml:math>-He collisions:<i>Ab initio</i>theory meets cavity-enhanced spectra

Słowiński, Michał; Thibault, Franck; Tan, Yan; Wang, Jin; Liu, Anwen; Hu, Shui-Ming; Kassi, S.; Campargue, A.; Konefał, Magdalena; Jóźwiak, Hubert; Patkowski, Konrad; Żuchowski, Piotr S.; Ciuryło, R.; Lisak, D.; Wcisło, Piotr

doi:10.1103/physreva.101.052705

Cited by 28 publications

(16 citation statements)

References 80 publications

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“…104 It has been recently shown for a benchmark system of helium-perturbed H 2 , that a full ab initio description of the shapes of rovibrational transitions leads to subpercent agreement with experimentally measured spectra. 105 This successful theoretical approach is based on a very accurate PES, determined from first principles, 106,107 quantum scattering calculations and a state-of-the-art model of collision-perturbed shape of rovibrational resonance, [108][109][110][111] which includes the speed dependence of line broadening and shift 112 and the influence of velocity changing collisions. 113 Helium-perturbed H 2 lines were subjects of several recent investigations.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

Ab initio investigation of the CO–N2 quantum scattering: The collisional perturbation of the pure rotational R(0) line in CO

Jóźwiak

Thibault

Cybulski

et al. 2021

The Journal of Chemical Physics

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We report fully quantum calculations of the collisional perturbation of a molecular line for a system that is relevant for Earth's atmosphere. We consider the N 2 -perturbed pure rotational R(0) line in CO. The results agree well with the available experimental data. This work constitutes a significant step towards populating the spectroscopic databases with ab initio collisional line-shape parameters for atmosphere-relevant systems. The calculations were performed using three different recently reported potential energy surfaces (PESs). We conclude that all three PESs lead to practically the same values of the pressure broadening coefficients.

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Section: Accepted Manuscriptmentioning

confidence: 99%

Ab initio investigation of the CO–N2 quantum scattering: The collisional perturbation of the pure rotational R(0) line in CO

Jóźwiak

Thibault

Cybulski

et al. 2021

The Journal of Chemical Physics

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“…[3][4][5][6]) which enable predictions of non-Voigt effects (including the influences of both the speed dependences and the collisioninduced velocity changes) on the profiles of collisionally-isolated lines with a typical accuracy of a few 0.1% (e.g. [4,[7][8][9][10]). Concerning the line-mixing (LM) process, its effects on spectra have been experimentally and theoretically studied for decades [1,2].…”

Section: Introductionmentioning

confidence: 99%

Toward measurements of the speed-dependence of line-mixing

Boulet

Hartmann

2021

Journal of Quantitative Spectroscopy and Radiative Transfer

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We theoretically demonstrate that some doublets of NH 3 broadened by Ar and heavier atoms may be suitable for the first experimental demonstration of a so-far unstudied problem: The spectral effects of the speed dependence of line-mixing. By using realistic assumptions and spectroscopic data from previous studies, we show that neglecting this process leads to errors on the spectral shape of up to 2% of the peak absorption value. When multispectrum fits are made assuming speed-independent line couplings, the peak-to-dip residuals amplitudes reduce to about 0.5% and 1% for NH 3 -Ar and -Xe, respectively. The magnitude of the effect is thus comparable to that of the speed dependence of the line broadening on isolated shapes, which has been demonstrated in many experimental studies. It should hence be detectable with high accuracy modern laboratory spectroscopic techniques. With this aim, guidelines and conditions paving the path for future experiments are given.

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“…Quantum-mechanical calculations of collisional dephasing have been performed for numerous systems [13,26], including CO-Ar [20,21,27,28]. In contrast, treatments accounting for both dephasing and the effects of VCs were mostly limited to the hydrogen molecule and its isotopologues [19,22,[29][30][31], which are not representative of systems relevant to atmospheric studies.…”

Section: Introductionmentioning

confidence: 99%

Subpercent agreement between ab initio and experimental collision-induced line shapes of carbon monoxide perturbed by argon

et al. 2020

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We present fully ab initio calculations of second-overtone rovibrational line shapes of carbon monoxide perturbed by argon. The quantum mechanical scattering problem between CO and Ar is solved numerically for two different ab initio interaction potentials. We use the generalized Hess method to determine spectroscopic cross sections which describe the effect of collisions on each spectral line. Using these cross sections, we determine the line-shape parameters that we use to generate the Hartmann-Tran and speed-dependent billiard ball profiles. We compare the generated line shapes with high-quality experimental line profiles of five lines measured at five pressures between 0.01 and 1 atm. A subpercent agreement over the entire pressure range is obtained. Calculations for the P(9) line are used to inspect the effects of the two interaction potentials. The discrepancies for both the considered interaction potentials and the experiment are explained within the described theoretical framework. The presented results are the most accurate collisional line-shape calculations for a system with collision dynamics representative of atmospherically relevant species.

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H2-He collisions:Ab initiotheory meets cavity-enhanced spectra

Cited by 28 publications

References 80 publications

Ab initio investigation of the CO–N2 quantum scattering: The collisional perturbation of the pure rotational R(0) line in CO

Ab initio investigation of the CO–N2 quantum scattering: The collisional perturbation of the pure rotational R(0) line in CO

Toward measurements of the speed-dependence of line-mixing

Subpercent agreement between ab initio and experimental collision-induced line shapes of carbon monoxide perturbed by argon

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