Rotational Structure in the A2Σ+, B2Σ+, and a4Σ− – X2Π Transitions of GeF

Abstract

Rotational analysis of over 50 sub-bands of three emission transitions of 74GeF has given vibrational and rotational constants for the four lowest-lying electronic states of GeF. One of these is a 4Σ− state in Hund's case (a), where all four spin components have been identified. Extensive perturbations between this 4Σ− state and the B2Σ+ state have been analyzed in detail: the two states appear to interact mainly by a second-order mechanism through the so far uncharacterized σπ22Σ+ state, but the surprisingly large J dependence of the perturbation matrix element suggests that another mechanism, possibly involving the ground state, may contribute. Further perturbations, where the lines show an unusual intensity enhancement, appear in those sub-bands with B2Σ+ ν = 4 as upper state.