'Institute of Electrical and Electronics Engineers (IEEE)'
Abstract
Even within the sudden approximation, the removal of one neutral Hartree-Fock orbital does not leave the molecule in a pure one-hole state of the cation; coupling to virtual orbitals leads to a breakdown in the molecular orbital picture. This can be understood as interaction with two-hole one-particle states (singly excited cations) and becomes significant when those states are energetically similar to the one-hole states. This splitting of states is most relevant for inner valence holes which lie above the double ionisation potential. As such, impulsive creation of an inner valence hole (IVH) wavepacket results in a time dependent charge density which is purely electronic in nature (charge migration) [1] , [2] , though it depends on the nuclear geometry at the time of excitation, and subsequent nuclear motion will result in decoherence [3]
