Auger type decay processes play a fundamental role in atomic/molecular spectroscopy, sur-
face analysis, radiation damage, etc. These transitions can be viewed as consisting of two steps.
Firstly, a high energy photon produces a hole in an inner electronic shell, emitting a photoelec-
tron with kinetic energy dependent on the incident photon. Then the hole is lled by a valence
electron and a second valence electron is emitted with energy dependent on the energy levels of
the singly and doubly charged ions and not the incident photon energy. Auger decay processes
are considered to be an important manifestation of electron correlation as they are only possible
because of electron-electron interactions.
Recently, Murnane and Kapteyn  have investigated Laser-Enabled Auger Decay (LEAD)
in the multi-photon regime for vacancies that are not energetic enough to undergo the normal
Auger decay. Here we show that if considered in the single-photon regime, the LEAD process
provides a valuable insight into electron correlation in the inner valence ionised states. Firstly,
we analyse the single photon LEAD for the 2s-ionised state in Ne . A detailed investigation of
the mechanism of this single-photon LEAD process reveals that it is only possible because the
initial 2s-1 one-hole state contains con gurations of the type two holes and an electron excited
to a high-energy orbital. The cross-section of the single-photon LEAD process becomes a direct
measure of this con guration mixing. We use the rst-principles algebraic diagrammatic con-
struction (ADC) scheme and the Stieltjes imaging technique to evaluate the single-photon
LEAD cross-sections in ns-ionised states of Ne and Ar. The correlation in the inner valence
ionised states of trans-1,3 Butadiene are investigated as they are an example of a molecule with
strong con guration mixing resulting in the breakdown of the molecular orbital (MO) picture
of ionisation. We show that the breakdown of the MO picture leads to a dramatic increase
of the single-photon LEAD cross-section relative to the atomic case. Finally, we propose that
single photon LEAD can be a sensitive experimental probe for the attosecond hole migration
triggered by the MO breakdown.
1 P. Ranitovic, X. M. Tong, C. W. Hogle, X. Zhou, Y. Liu, N. Toshima, M. M. Murnane,
H. C. Kapteyn, Phys. Rev. Lett. 106, 053002 (2011).
2 See e.g. K. Gokhberg, V. Vysotskiy, L. S. Cederbaum, L. Storchi, F. Tarantelli, V. Averbukh,
J. Chem. Phys. 130, 064104 (2009).
3 L. S. Cederbaum, W. Domcke, J. Schirmer, W. Von Niessen, Adv. Chem. Phys. 65, 115