Abstract
ABSTRACTThe pulsed-field-ionisation zero-kinetic-energy photoelectron spectrum of the origin band of the ionising transition of propyne has been recorded at a resolution sufficient to partially resolve the rotational structure. The rovibronic photoionisation selection rules are derived in the spin double group C3v(MS)2 and are used to model the experimental spectrum and determine the adiabatic ionisation energy of propyne and the spin-orbit coupling constant of the radical cation of propyne. The Jahn–Teller effect is found to significantly affect the spin-orbit splitting of the cationic ground state.
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