We present quantum dynamics calculations showing that the electron-correlation-driven charge migration occurring in the correlation band of ionized molecules can lead to a redistribution of the charge which increases the stability of the system. These calculations offer an interpretation of recent experimental results obtained for adenine for which the stabilization induced by the electron-correlation-driven charge migration leads to a modification of the fragmentation pattern of the molecule after subsequent ionization. We argue that this charge-migration-induced stabilization is a general mechanism and discuss its implications for the development of attochemistry and how it can be understood in the context of the ultrafast, nonadiabatic relaxation taking place in highly excited molecular cations.

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• Ultrafast phenomena
• Molecules