We show that the complete photoemission dynamics in situations of electron-ion entanglement can be retrieved from photoelectron spectral measurements without information on the ion. To this end, we develop an energy-time analysis of the photoelectron's reduced density matrix based on first principles. We test and assess our approach with numerical simulations on a low-dimensional model molecule in interaction with broadband composite pulses concealing the vibrational resolution. Our method is directly applicable to recent experimental schemes measuring the photoelectron reduced density matrices in atomic and molecular photoemission. Therefore, it opens a new window on the dynamics of decoherence and entanglement at the attosecond timescale.

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• Atomic & molecular processes in external fields
• Electron wave interferometry
• Electronic excitation & ionization
• Photoemission
• Single- and few-photon ionization & excitation
• Ultrafast optics
• Ultrafast phenomena
• Vibronic effects