An extensive analysis of Ti and Fe emission spectra from both plane and hollow cathode glow discharges in argon in Grimm-type geometry, measured by high resolution Fourier transform spectrometer has allowed a novel comparison of excitation mechanisms. Deviations from simple models of laboratory plasmas assuming local thermodynamic equilibrium are observed. Analyte ionization in both discharge modes is dominated by charge transfer (CT) between Ar⁺ ions and neutral analyte atoms, while this process is more pronounced in a plane cathode than hollow cathode discharge. Radiative decay of the CT-excited levels is found to cause overpopulation of long-lived ground term and metastable analyte ions, relative to the equilibrium number densities that would be expected from the Saha-Boltzmann distribution. This overpopulation is found to spread into high-energy levels of neutral atoms by collisional 3-body recombination with electrons. Lower atomic levels of the analytes are excited by collisions with electrons, the number density of which is not high enough to support conditions close to local thermodynamic equilibrium. The analysis of the spectra is based on experimental Boltzmann plots, transition rate diagrams and intensity ratios of emission lines measured in both discharge configurations. Uncertainty propagation in the data processing procedures is analyzed and described.

用高分辨率傅里叶变换光谱仪对氩气中格林和格林的平面和空心阴极辉光放电的Ti和Fe发射光谱进行了广泛的分析，从而对激发机理进行了新颖的比较。观察到与假设局部热力学平衡的实验室血浆简单模型的偏差。两种放电模式下的分析物电离均以Ar ⁺之间的电荷转移（CT）为主离子和中性分析物原子，而此过程在平面阴极中比空心阴极放电更为明显。发现相对于萨哈-玻耳兹曼分布所期望的平衡数密度，CT激发能级的辐射衰减会导致长期存在的地面术语和亚稳定的分析物离子的过度聚集。通过与电子的碰撞3体重组，发现了这种过量种群扩散到高能级的中性原子。与电子的碰撞激发了较低原子水平的分析物，电子的数量密度不足以支持接近局部热力学平衡的条件。光谱分析基于实验的玻耳兹曼图，跃迁速率图和在两种放电配置下测得的发射线强度比。