Search for long-lasting electronic coherence using on-the-fly ab initio semiclassical dynamics

Area of Science:

• Quantum chemistry
• Molecular dynamics
• Physical chemistry

Background:

• Electronic coherence plays a crucial role in molecular processes.
• Understanding electron dynamics after ionization is key to controlling chemical reactions.

Purpose of the Study:

• To search for small polyatomic molecules exhibiting long-lasting electronic coherence after outer-valence ionization.
• To investigate the dynamics of electronic coherence coupled to nuclear motion in unexplored molecules.

Main Methods:

• Utilized high-level ab initio electronic structure calculations.
• Employed efficient on-the-fly semiclassical evaluation of nuclear dynamics.
• Performed extensive computational scans of small polyatomic molecules.

Main Results:

• Most molecules showed rapid damping of electronic coherence (within a few femtoseconds) due to nuclear rearrangement.
• Identified several novel molecules with sustained electronic coherence lasting up to 10 femtoseconds.
• Presented full-dimensional simulations of coupled electron-nuclear dynamics for previously studied molecules.

Conclusions:

• The study identifies promising candidates for experimental observation of long-lived electronic coherences.
• Highlights the importance of considering coupled nuclear motion in electron dynamics.
• Advances the understanding of quantum phenomena in small molecules relevant to chemical reactivity.