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Understanding Charge Dynamics in Dense Electronic Manifolds in Complex Environments

Fulvio Perrella, Alessio Petrone, Nadia Rega

2023Journal of Chemical Theory and Computation21 citationsDOIOpen Access PDF

Abstract

", 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.

Topics & Concepts

Chemical physicsElectronic structureElementary chargeMolecular dynamicsUltrashort pulseMoleculeChemistryExcited stateCharge (physics)Density functional theoryMaterials scienceComputational chemistryPhysicsElectronAtomic physicsQuantum mechanicsOrganic chemistryLaserPhotochemistry and Electron Transfer StudiesSpectroscopy and Quantum Chemical StudiesFree Radicals and Antioxidants
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