Cavity ringdown spectroscopy of atmospherically important radicals

Many radicals, due to their electronic structure, have low-lying electronic state transitions to which lie in the near-IR. These transitions even in the most important atmospheric radicals have not been thoroughly investigated due to their weakness and low attainable concentrations of radicals. This thesis describes the application of cavity ringdown spectroscopy to detection of near-IR states of some atmospherically important radicals.; The near-IR cavity ringdown spectrometer constructed for these experiments is described in detail in chapter 1. The pulsed near-IR laser radiation was generated by sequential Raman shifting of the output of a tunable dye laser in hydrogen. The constructed multi-pass Raman cell extended the tunable range of the available dye laser continuously from the visible to 6000 cm -1 with 0.15 cm-1 resolution.; In chapter 2, the near-IR spectra of chloro-ethyl, -propyl, -butyl and -butenyl peroxy radicals in the 7000--8600 cm-1 region are reported. The origin bands of the electronic transition were found to be shifted by 200 cm-1 to the red. The spectra have more complex structure than those of unsubstituted homologues. DFT calculations predicted multiple conformers for C2H4ClO2 and C3H6ClO2 with the energies within 2 kcal/mol. Tentative assignment of the C2H4ClO2 spectrum is presented. The integrated cross-section for the transition in chloro-ethyl peroxy radical is estimated from the known rate of self-reaction.; In chapter 3, the first full absorption spectrum of the "dark" A 2E″ ← X˜ 2A'2 transition of the nitrate radical NO3 in the 6000--10700 cm-1 region is reported. nu2, nu3, and nu 4 progressions and several combination bands are assigned. A more accurate estimate for the position of the "dark" origin is given. Analysis of the partially resolved rotational contours suggests that NO3 undergoes static Jahn-Teller distortion in some of the vibronic states.