MolTech-Anjou, UMR CNRS 6200, Université d'Angers, 2 boulevard Lavoisier, 49045 Angers, France.
J Chem Phys. 2011 Jun 14;134(22):224301. doi: 10.1063/1.3596750.
A line-mixing shape analysis of the isotropic remnant Raman spectrum of the 2ν(3) overtone of CO(2) is reported at room temperature and for densities, ρ, rising up to tens of amagats. The analysis, experimental and theoretical, employs tools of non-resonant light scattering spectroscopy and uses the extended strong collision model (ESCM) to simulate the strong line mixing effects and to evidence motional narrowing. Excellent agreement at any pressure is observed between the calculated spectra and our experiment, which, along with the easy numerical implementation of the ESCM, makes this model stand out clearly above other semiempirical models for band shape calculations. The hitherto undefined, explicit ρ-dependence of the vibrational relaxation rate is given. Our study intends to improve the understanding of pressure-induced phenomena in a gas that is still in the forefront of the news.
报道了室温下 CO（2）2ν（3）泛频的各向同性剩余喇曼光谱的混合线形状分析，密度 ρ 上升到数十大气压。分析采用非共振光散射光谱学的工具，并使用扩展强碰撞模型（ESCM）来模拟强线混合效应并证明运动变窄。在任何压力下，计算光谱与我们的实验都非常吻合，这与 ESCM 的易于数值实现相结合，使得该模型明显优于其他用于带形状计算的半经验模型。给出了迄今未定义的振动弛豫率的明确的 ρ 依赖性。我们的研究旨在提高对这种仍然处于新闻前沿的气体中压力诱导现象的理解。
