| Autor: |
Sifain AE, Bjorgaard JA, Nelson TR, Nebgen BT, White AJ, Gifford BJ; Department of Chemistry and Biochemistry , North Dakota State University , Fargo , North Dakota 58108 , United States., Gao DW; Los Alamos High School , Los Alamos , New Mexico 87544 , United States., Prezhdo OV, Fernandez-Alberti S; Universidad Nacional de Quilmes/CONICET , Roque Saenz Peña 352 , B1876BXD Bernal , Argentina., Roitberg AE; Department of Chemistry , University of Florida , Gainesville , Florida 32611 , United States., Tretiak S |
| Abstrakt: |
Solvation can be modeled implicitly by embedding the solute in a dielectric cavity. This approach models the induced surface charge density at the solute-solvent boundary, giving rise to extra Coulombic interactions. Herein, the Nonadiabatic EXcited-state Molecular Dynamics (NEXMD) software was used to model the photoexcited nonradiative relaxation dynamics in a set of substituted donor-acceptor oligo( p-phenylenevinylene) (PPVO) derivatives in the presence of implicit solvent. Several properties of interest including optical spectra, excited state lifetimes, exciton localization, excited state dipole moments, and structural relaxation are calculated to elucidate dependence of functionalization and solvent polarity on photoinduced nonadiabatic dynamics. Results show that solvation generally affects all these properties, where the magnitude of these effects vary from one system to another depending on donor-acceptor substituents and molecular polarizability. We conclude that implicit solvation can be directly incorporated into nonadiabatic simulations within the NEXMD framework with little computational overhead and that it qualitatively reproduces solvent-dependent effects observed in solution-based spectroscopic experiments. |
