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Synthesis of ab initio and effective Hamiltonian line lists for ozone
Journal of Quantitative Spectroscopy and Radiative Transfer ( IF 2.3 ) Pub Date : 2021-03-22 , DOI: 10.1016/j.jqsrt.2021.107651
David Jacquemart , Vladimir Yu. Makhnev , Nikolai F. Zobov , Jonathan Tennyson , Oleg L. Polyansky

A synthetic line list for the ozone molecule is presented. Variational calculation using the semi-empirical potential energy surface (PES) and ab initio dipole moment surface (DMS) produce very accurate values of line intensities, but give line positions far away from their experimental values. Furthermore assignment of approximate rotational and vibrational quantum numbers are missing from variationally calculated line list. Effective Hamiltonian calculations are complimentary to ab initio line lists in these properties giving excellent value of line positions, close to experimental ones, and a full set of quantum numbers assignment. The synthesis of both these qualities in one line list is highly desirable. Here a synthetic line list for 16O3 is presented. The method of corrections of distorted intensities in variational linelist with ab initio DMS due to the artificial intensity stealing is developed and applied. Comparison of the synthetic line list with all major published line lists and available experimental data is given. The calculated line intensities agree to within experimental error for most bands for which accurate measurements are available.



中文翻译:

臭氧的从头算和有效哈密顿线列表的合成

给出了臭氧分子的合成路线清单。使用半经验势能面(PES)和从头算起的偶极矩表面(DMS)进行的变分计算会产生非常精确的线强度值,但线位置会偏离其实验值。此外,从可变计算的线列表中缺少近似的旋转和振动量子数的分配。在这些特性中,有效的哈密顿量计算是从头算线列表的补充,可提供极佳的线位置值,接近实验值以及完整的量子数分配。高度希望将这两种质量综合在一个行列表中。这是针对的综合线路列表16Ø3被表达。开发并应用了从头开始的DMS校正由于人工强度窃取而引起的变线表失真强度校正的方法。给出了合成线列表与所有主要公开线列表的比较以及可用的实验数据。对于可进行精确测量的大多数频段,计算得出的线强度均在实验误差范围内。

更新日期:2021-04-08
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