Charge Migration Manifests as Attosecond Solitons in Conjugated Organic Molecules

Francois Mauger (1) , Aderonke S Folorunso (2) , Kyle A Hamer (1) , Cristel Chandre (3) , Mette B Gaarde (1) , Kenneth Lopata (4, 5) , Kenneth J Schafer (1)

1 Department of Physics and Astronomy [Baton Rouge]
2 Department of Chemistry
3 I2M - Institut de Mathématiques de Marseille
4 Department of Chemistry
5 CCT - Center for Computation and Technology [Baton Rouge]

We report theoretical investigations of charge migration that takes place along the backbone of conjugated hydrocarbons, simulated using time-dependent density functional theory and analyze using tools from nonlinear dynamics. In this electron-density framework charge migration modes emerge as attosecond solitons and the same type of solitary-wave dynamics manifests in full molecular simulations and in a simplified model of the conjugated $\pi$ system. These attosecond-soliton modes result from a balance between dispersion and nonlinear effects tied to time-dependent multi-electron interactions. The soliton-mode mechanism, and the nonlinear tools we use to analyze it, pave the way for understanding migration dynamics in a broad range of organic molecules. For instance, we demonstrate the opportunities for chemically steering charge migration via molecular functionalization, which can alter both the initially localized electron perturbation and its subsequent time evolution.

Domaines: Physique Atomique [physics.atom-ph]; Chimie-Physique [physics.chem-ph]; Dynamique Chaotique [nlin.CD]

Francois Mauger, Aderonke S Folorunso, Kyle A Hamer, Cristel Chandre, Mette B Gaarde, et al.. Charge Migration Manifests as Attosecond Solitons in Conjugated Organic Molecules. 2021. ⟨hal-02866922v2⟩