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Abstract

In a molecular Auger spectrum information on the decaying state is implicitly ensemble-averaged. For a repulsive core-ionized state, for example, contributions from all parts of its potential curve are superimposed in the Auger spectrum. Using carbon tetrafluoride (CF₄, tetrafluoromethane), we demonstrate for the first time that these contributions can be disentangled by recording photoelectron–Auger electron coincidence spectra with high energy resolution. For the F K-VV spectrum of CF₄, there are significant differences in the Auger decay at different intermediate state (single core hole) geometries. With the help of calculations, we show that these differences result primarily from zero-point fluctuations in the neutral molecular ground state, but are amplified by the nuclear dynamics during Auger decay.