Kinetics of OH Radicals from Flame Emission Spectra. I. Vibrational Transition Probabilities, Intensities, and Equilibrium in the 2Σ+—2Π Transition

Abstract

The relative vibrational transition probabilities for the first four vibrational levels of the ²Σ⁺—²Π system of OH have been calculated. Anharmonic wave functions derivable from the Morse potential function were used and the electronic dipole moment matrix component appearing in this formulation has been evaluated. Relative intensities for the various bands have been calculated under the assumption of thermal equilibrium. Comparison of these calculated values with the data of Dieke and Crosswhite on the oxy‐acetylene flame at one atmosphere indicate vibrational equilibrium with a vibrational temperature of ∼3750°K in the outer cone which compares with a rotational temperatue of ∼3000°K. The relationship between vibrational and rotational equilibrium for this case is discussed briefly.