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

• Main Authors: Scheidegger, Alan, Vaníček, Jiří, Golubev, Nikolay V
• Format: Journal Article
• Language: English
• Published: 26-10-2021
• Subjects: Physics - Chemical Physics
• DOI: 10.48550/arxiv.2110.13904

J. Chem. Phys. 156, 034104 (2022) Using a combination of high-level ab initio electronic structure methods with
efficient on-the-fly semiclassical evaluation of nuclear dynamics, we performed
a massive scan of small polyatomic molecules searching for a long lasting
oscillatory dynamics of the electron density triggered by the outer-valence
ionization. We observed that in most of the studied molecules, the sudden
removal of an electron from the system either does not lead to the appearance
of the electronic coherence, or the created coherences become damped by the
nuclear rearrangement on a time scale of a few femtoseconds. However, we report
several so far unexplored molecules with the electronic coherences lasting up
to 10 fs which can be good candidates for experimental studies. In addition, we
present the full-dimensional simulations of the electronic coherences coupled
to nuclear motion in several molecules which were studied previously only in
the fixed nuclei approximation.