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Sub-percent agreement betweenab initioand experimental collision-induced line shapes of carbon monoxide perturbed by argon
Physical Review A ( IF 2.9 ) Pub Date : 
Grzegorz Kowzan, Hubert Cybulski, Piotr Wcisło, Michał Słowiński, Alexandra Viel, Piotr Masłowski, Franck Thibault

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 on 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 sub-percent agreement in 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 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.

中文翻译:

从头算起和氩气对一氧化碳的实验碰撞诱发的一氧化碳线形之间的一致性不足

我们介绍了由氩气扰动的一氧化碳的二次谐波旋转振动线形的从头算。在两个不同的从头算起的相互作用势上,数值地解决了CO和Ar之间的量子力学散射问题。我们使用广义Hess方法来确定光谱截面,该截面描述了碰撞对每条光谱线的影响。使用这些横截面,我们确定用于生成Hartmann-Tran和速度相关的台球轮廓的线形参数。我们将生成的线形与在0.01和1 atm的五个压力下测得的五条线的高质量实验线轮廓进行比较。在整个压力范围内获得了不到百分之百的一致性。P(9)线的计算用于检查两个相互作用势的影响。在所描述的理论框架内解释了所考虑的相互作用电位和实验的差异。给出的结果是具有碰撞动力学代表大气相关物种的系统的最精确碰撞线形状计算。
更新日期:2020-07-13
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