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Issue 4, 2016
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Photoelectron diffraction in methane probed via vibrationally resolved inner-valence photoionization cross-section ratios

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Abstract

Vibrationally resolved photoionization of the 2a1 orbital in methane has been studied both experimentally and theoretically, over a wide range of photon energies (40–475 eV). A vibrational progression associated with the symmetric stretch mode of the 2a1−1 single-hole state was observed in the experimental photoelectron spectra. Individual vibrational sub-states of the spectra were found to be best modeled by asymmetric line-shapes with linewidths gradually increasing with the vibrational quantum number. This indicates the occurrence of a pre-dissociation process for the involved ionic state, discussed here in detail. Finally, diffraction patterns were observed in the vibrational branching ratios for the first three vibrational sub-states (“v-ratios”) of the experimental photoelectron spectra. They are found to be in excellent qualitative agreement with those obtained from ab initio models. Compared with previous studies of the 1a1−1 core–shell photoionization of methane, the period of oscillation of the v-ratios is found to be very different and the phases are of opposite signs. This suggests a strong interplay between the electron diffraction and interference effects inside the molecular potential.

Graphical abstract: Photoelectron diffraction in methane probed via vibrationally resolved inner-valence photoionization cross-section ratios

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Article information


Submitted
16 Nov 2015
Accepted
17 Dec 2015
First published
22 Dec 2015

Phys. Chem. Chem. Phys., 2016,18, 3214-3222
Article type
Paper
Author version available

Photoelectron diffraction in methane probed via vibrationally resolved inner-valence photoionization cross-section ratios

S. Nandi, E. Plésiat, M. Patanen, C. Miron, J. D. Bozek, F. Martín, D. Toffoli and P. Decleva, Phys. Chem. Chem. Phys., 2016, 18, 3214
DOI: 10.1039/C5CP07017A

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