Attochemical Control of Nuclear Motion despite Fast Electronic Decoherence

Area of Science:

• Physical Chemistry
• Quantum Dynamics
• Molecular Spectroscopy

Background:

• Attosecond and femtosecond pulses create molecular electronic coherences.
• Charge migration describes ultrafast electron oscillations.
• The influence of short-lived electronic dynamics on nuclear motion is largely unknown.

Purpose of the Study:

• To investigate if brief electronic coherences can affect longer-timescale nuclear rearrangements.
• To simulate coupled electron-nuclear dynamics in ethylene.

Main Methods:

• Full-dimensional quantum dynamics simulations.
• Modeling ionization and coherent excitation of ethylene.
• Analyzing electron and vibrational coherences.

Main Results:

• Electronic coherences in ethylene exhibit half-lives under 1 femtosecond.
• These short-lived electronic coherences induce vibrational coherences lasting over 50 femtoseconds.
• Derivative coupling vectors are key pathways for this influence.

Conclusions:

• Short-lived electronic coherences can have lasting effects on molecular nuclear motion.
• Findings are crucial for interpreting attosecond experimental data.
• Potential for developing attochemical control strategies is highlighted.