School of Chemistry, University of Bristol, Bristol, United Kingdom.
J Phys Chem A. 2011 Feb 10;115(5):774-83. doi: 10.1021/jp109894x. Epub 2011 Jan 4.
Cavity ring-down spectroscopy using a fiber-coupled continuous wave distributed feedback laser at a wavelength of 1520 nm has been used to measure extinction of light by samples of nearly monodisperse aerosol particles <1 μm in diameter. A model is tested for the analysis of the sample extinction that is based on the Poisson statistics of the number of particles within the intracavity laser beam: variances of measured extinction are used to derive values of the scattering cross section for size-selected aerosol particles, without need for knowledge of the particle number density or sample length. Experimental parameters that influence the performance of the CRD system and the application and limitations of the statistical model are examined in detail. Determinations are reported of the scattering cross sections for polystyrene spheres (PSSs), sodium chloride, and ammonium sulfate, and, for particles greater than 500 nm in diameter, are shown to be in agreement with the corresponding values calculated using Mie theory or Discrete Dipole Approximation methods. For smaller particles, the experimentally derived values of the scattering cross section are larger than the theoretical predictions, and transmission of a small fraction of larger particles into the cavity is argued to be responsible for this discrepancy. The effects of cubic structure on the determination of optical extinction efficiencies of sodium chloride aerosol particles are examined. Values are reported for the real components of the refractive indices at 1520 nm of PSS, sodium chloride, and ammonium sulfate aerosol particles.
利用波长为 1520nm 的光纤耦合连续波分布反馈激光器的光腔衰荡光谱技术已被用于测量直径小于 1μm 的近单分散气溶胶粒子对光的消光。本文测试了一种用于分析样品消光的模型,该模型基于腔内激光束内粒子数的泊松统计:通过测量消光的方差,可以推导出经尺寸选择的气溶胶粒子的散射截面值,而无需了解粒子数密度或样品长度。详细研究了影响 CRD 系统性能的实验参数以及统计模型的应用和局限性。报告了聚苯乙烯球(PSS)、氯化钠和硫酸铵的散射截面的测定值,并且对于直径大于 500nm 的粒子,与使用 Mie 理论或离散偶极子近似方法计算得到的相应值是一致的。对于较小的粒子,实验得出的散射截面值大于理论预测值,据认为是一小部分较大的粒子进入腔体内导致了这种差异。还研究了立方结构对氯化钠气溶胶粒子光吸收效率测定的影响。报告了 PSS、氯化钠和硫酸铵气溶胶粒子在 1520nm 处的折射率实部的值。