Chai Shijie, Yang Dongzheng, Zhou Yanzi, Xie Daiqian
Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.
Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA.
J Chem Phys. 2023 Oct 28;159(16). doi: 10.1063/5.0170148.
This work studied the rovibrational absorption spectral line-shape parameters of the P(1)-P(10) and R(0)-R(9) lines for Hydrogen fluoride perturbed by argon in the 0-0, 1-0, and 2-0 vibrational bands at 20-1000 K. A dataset of beyond-Voigt line-shape parameters (pressure broadening and shifting parameters, their speed dependencies, and the complex Dicke parameters) has been theoretically determined for the first time from generalized spectroscopic cross-section calculated by the full quantum scattering calculations. Then these parameters were employed to predict the line shape and asymmetry based on the partially-correlated speed-dependent hard-collision and the partially-correlated quadratic-speed-dependent hard-collision profiles. The effect of each parameter on the line shape and line asymmetry was further studied, which revealed that the beyond-Voigt effects were indispensable to accurately describe the line shape contour. Our results are in good agreement with the available experimental observations and provide a comprehensive set of theoretical references for further experimental measurements.
本研究工作针对在20 - 1000 K温度下，处于0 - 0、1 - 0和2 - 0振动带中被氩气扰动的氟化氢，研究了P(1) - P(10)和R(0) - R(9)谱线的振转吸收光谱线形参数。首次通过全量子散射计算得到的广义光谱截面，从理论上确定了一组超越夫琅禾费线形参数数据集（压力展宽和频移参数、它们的速度依赖性以及复狄克参数）。然后，基于部分相关的速度依赖硬碰撞和部分相关的二次速度依赖硬碰撞轮廓，利用这些参数预测谱线形状和不对称性。进一步研究了每个参数对谱线形状和谱线不对称性的影响，结果表明超越夫琅禾费效应对于准确描述谱线形状轮廓是不可或缺的。我们的结果与现有的实验观测结果吻合良好，并为进一步的实验测量提供了一套全面的理论参考。
