Gas-Phase Electron Resonance Spectra of Fluorine and Chlorine Atoms in Their Ground (P322) and Excited (2P½) Electronic States

Abstract

The gas-phase electron resonance spectra of fluorine and chlorine atoms in their ground (P322) and excited (2P½) states are described. Fluorine atoms are formed by passing CF4 through a microwave discharge; the P322 spectrum shows six strong lines and five weaker lines, three of the latter being previously unreported and arising from ΔMF=0 transitions. Two lines of the 2P½ spectrum are detected and their intensity relative to that of the ground-state spectrum indicates a non-Boltzmann distribution between the P322 and 2P½ states. Chlorine atoms are formed by passing CF3Cl or CF3Cl/Cl2 mixtures through a microwave discharge. In addition to the intense 35Cl and 37Cl P322 spectra, four weak lines arising from excited 35Cl 2P½ atoms are detected. The intensities of these lines also indicate a non-Boltzmann distribution between the ground and excited states.