Understanding Charge Dynamics in Dense Electronic Manifolds in Complex Environments

Fulvio Perrella; Alessio Petrone; Nadia Rega

doi:10.1021/acs.jctc.2c00794

Understanding Charge Dynamics in Dense Electronic Manifolds in Complex Environments

J Chem Theory Comput. 2023 Jan 5;19(2):626-639. doi: 10.1021/acs.jctc.2c00794. Online ahead of print.

Authors

Fulvio Perrella¹, Alessio Petrone^{1

2

3}, Nadia Rega^{1

2

3

4}

Affiliations

¹ Department of Chemical Sciences, University of Napoli Federico II, Complesso Universitario di M.S. Angelo, via Cintia 21, I-80126, Napoli, Italy.
² Scuola Superiore Meridionale, Largo San Marcellino 10, I-80138, Napoli, Italy.
³ Istituto Nazionale Di Fisica Nucleare, sezione di Napoli, Complesso Universitario di Monte S. Angelo ed. 6, via Cintia, 80126, Napoli, Italia.
⁴ CRIB, Centro Interdipartimentale di Ricerca sui Biomateriali, Piazzale Tecchio 80, I-80125, Napoli, Italy.

Abstract

Photoinduced charge transfer (CT) excited states and their relaxation mechanisms can be highly interdependent on the environment effects and the consequent changes in the electronic density. Providing a molecular interpretation of the ultrafast (subpicosecond) interplay between initial photoexcited states in such dense electronic manifolds in condensed phase is crucial for improving and understanding such phenomena. Real-time time-dependent density functional theory is here the method of choice to observe the charge density, explicitly propagated in an ultrafast time domain, along with all time-dependent properties that can be easily extracted from it. A designed protocol of analysis for real-time electronic dynamics to be applied to time evolving electronic density related properties to characterize both in time and in space CT dynamics in complex systems is here introduced and validated, proposing easy to be read cross-correlation maps. As case studies to test such tools, we present the photoinduced charge-transfer electronic dynamics of 5-benzyluracil, a mimic of nucleic acid/protein interactions, and the metal-to-ligand charge-transfer electronic dynamics in water solution of [Ru(dcbpy)₂(NCS)₂]^4-, dcbpy = (4,4'-dicarboxy-2,2'-bipyridine), or "N3^4-", a dye sensitizer for solar cells. Electrostatic and explicit ab initio treatment of solvent molecules have been compared in the latter case, revealing the importance of the accurate modeling of mutual solute-solvent polarization on CT kinetics. We observed that explicit quantum mechanical treatment of solvent slowed down the charge carriers mobilities with respect to the gas-phase. When all water molecules were modeled instead as simpler embedded point charges, the electronic dynamics appeared enhanced, with a reduced hole-electron distance and higher mean velocities due to the close fixed charges and an artificially increased polarization effect. Such analysis tools and the presented case studies can help to unveil the influence of the electronic manifold, as well as of the finite temperature-induced structural distortions and the environment on the ultrafast charge motions.