High Resolution Electronic Spectra of Inorganic Molecules. The Structure and Spectrum of Chlorine Dioxide

摘要

Bands of the 4750 A system of chlorine dioxide have been analyzed rotationally. Results from the well-resolved sub-bands establish that these are parallel bands and hence, as the ground state is known from microwaves to be 2B1, that the excited state is 2A2. The transition (100) - (000) analyzed in most detail has v(o) = 21722/cm and gives the upper state rotational constants. Quadratic, cubic and quartic potential constants have also been obtained for the 2A2 state. The cubic force constants are used to compute the vibration-rotation interaction constants and hence to calculate equilibrium values of the upper state rotational constants. The cubic and quartic force constants together enter into expressions for the anharmonic vibrational wavefunctions. Wavefunctions of this type are used to calculate relative intensities in the electronic band system.