Spectroscopic analysis of asymmetric top free radicals——Application to pure rotational spectra of NO_2 in the ground vibronic state

Several key problems involved in the analyses of spectra of asymmetric top molecules, i.e., the effective Hamiltonian, the representation and basis vector, identification of energy levels, the selection rules, the relative intensity, and Zeeman tuning rate, were elucidated systematically. Introducing the high-order centrifugal distortion terms into the effective Hamiltonian, the precision for calculation has been improved substantially, which allows us to analyze the high-lying rotational transitions. A global analysis of all available spectra of 14N16O2 in the ground vibronic state has been made to obtain a set of molecular constants of 14N16O2 in the ground vibronic state which is the most precise and extensive so far. Using the improved parameters, some FIR LMR lines left unassigned hitherto have been identified successfully.