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Conformational and nuclear dynamics effects in molecular Auger spectra: fluorine core-hole decay in CF4

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Lischke,  T.
Physical Chemistry, Fritz Haber Institute, Max Planck Society;

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Bradshaw,  Alexander M.
Theory, Fritz Haber Institute, Max Planck Society;
Max-Planck-Institut für Plasmaphysik, EURATOM Association;

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Citation

Arion, T., Takahashi, O., Püttner, R., Ulrich, V., Barth, S., Lischke, T., et al. (2014). Conformational and nuclear dynamics effects in molecular Auger spectra: fluorine core-hole decay in CF4. Journal of Physics B, 47(12): 124033. doi:10.1088/0953-4075/47/12/124033.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0019-D7D5-F
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.