Photoexcited Nonadiabatic Dynamics of Solvated Push–Pull π‑Conjugated Oligomers with the NEXMD Software

• Published in: Journal of chemical theory and computation Vol. 14; no. 8; pp. 3955 - 3966
• Main Authors: Sifain, Andrew E., Bjorgaard, Josiah A., Nelson, Tammie R., Nebgen, Benjamin T., White, Alexander J., Gifford, Brendan J., Gao, David W., Prezhdo, Oleg V., Fernandez-Alberti, Sebastian, Roitberg, Adrian E., Tretiak, Sergei
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 14-08-2018
• Subjects: Charge density; Computer simulation; Dependence; Dipole moments; Excitation spectra; Molecular dynamics; Oligomers; Optical properties; Polarity; Software; Solvation; Solvents; Surface charge
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.8b00103

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.