PYROLYSIS JET SPECTROSCOPY AND AB-INITIO STUDIES OF THE S-1 AND T-1 STATES OF GERMANIUM DIFLUORIDE

Spectra of jet-cooled germanium difluoride were obtained by the reacti on of germanium metal and fluorine in the throat of a heated supersoni c jet. Two band systems at 331-305 and 231-224 nm were observed by las er-induced emission excitation spectroscopy. On the basis of high qual ity ab initio predictions of the energies, geometries and vibrational frequencies of the;lower electronic states, the two band systems are a ssigned as ($) over tilde a(3)B(1)-($) over tilde X(1)A(1) and ($) ove r tilde A(1)B(1) ($) over tilde X(1)A(1), respectively. The T-1-S-0 sp ectrum consists of a long, well-resolved progression in the excited st ate bending frequency with nu'(2) = 192.2 cm(-1) and T-00=30 582.1.cm( -1). The S-1-S-0 spectrum is a complex tangle of vibronic structure ac companied by a rising background. A partial analysis of the vibronic s tructure gave nu'(2) = 159.6 cm(-1) and T-00= 43 860.9 cm(-1). The spe ctra are very similar to the analogous band. systems of GeCl2.