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

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, either the sudden removal of an electron from the system 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.& nbsp;(c) 2022 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).

Automated summary

By using advanced computational methods and efficient nuclear dynamics evaluation, we conducted a comprehensive study on small polyatomic molecules with long-lasting oscillatory dynamics of electron density triggered by outer-valence ionization. We found that in most molecules, the sudden removal of an electron either does not lead to the appearance of electronic coherence or the created coherences are quickly damped by nuclear rearrangement within a few femtoseconds. However, we identified several unexplored molecules with electron coherences lasting up to 10 fs, which can be promising candidates for experimental studies. Furthermore, we performed full-dimensional simulations of electron coherences coupled with nuclear motion in several molecules that were previously only studied under the fixed nuclei approximation.