Decoherence and revival in attosecond charge migration driven by non-adiabatic dynamics

Attosecond charge migration is a periodic evolution of the charge density at specific sites of a molecule on a timescale defined by the energy intervals between the electronic states involved. Here we report the observation of charge migration in neutral silane (SiH4) in 690 as, its decoherence within 15 fs and its revival after 40-50 fs, using X-ray attosecond transient-absorption spectroscopy. We observe the migration of charge as pairs of quantum beats with a characteristic spectral phase in the transient spectrum, in agreement with theory. The decay and revival of the degree of electronic coherence is found to be a result of both adiabatic and non-adiabatic dynamics in the populated Rydberg and valence states. The experimental results are supported by fully quantum-mechanical ab initio calculations that include both electronic and nuclear dynamics, which additionally support the experimental evidence that conical intersections can mediate the transfer of electronic coherence from an initial superposition state to another one involving a different lower-lying state. X-ray ultrafast transient absorption spectroscopy captures the charge migration in neutral silane molecules, which shows in the spectra as pairs of quantum beats.

Automated summary

This study reports the observation of charge migration in neutral silane molecules using X-ray attosecond transient-absorption spectroscopy. The experimental results are supported by quantum-mechanical ab initio calculations, revealing the dynamics and mechanism of this migration phenomenon.