The European Physical Journal Special Topics

, Volume 225, Issue 8–9, pp 1743–1756 | Cite as

Solvent effects on optical excitations of poly para phenylene ethynylene studied by QM/MM simulations based on many-body Green's functions theory

  • B. Bagheri
  • M. Karttunen
  • B. Baumeier
Open Access
Regular Article Specific Models to Tackle Fundamental Questions
Part of the following topical collections:
  1. Modern Simulation Approaches in Soft Matter Science: From Fundamental Understanding to Industrial Applications


Electronic excitations in dilute solutions of poly para phenylene ethynylene (poly-PPE) are studied using a QM/MM approach combining many-body Green's functions theory within the GW approximation and the Bethe-Salpeter equation with polarizable force field models. Oligomers up to a length of 7.5 nm (10 repeat units) functionalized with nonyl side chains are solvated in toluene and water, respectively. After equilibration using atomistic molecular dynamics (MD), the system is partitioned into a quantum region (backbone) embedded into a classical (side chains and solvent) environment. Optical absorption properties are calculated solving the coupled QM/MM system self-consistently and special attention is paid to the effects of solvents. The model allows to differentiate the influence of oligomer conformation induced by the solvation from electronic effects related to local electric fields and polarization. It is found that the electronic environment contributions are negligible compared to the conformational dynamics of the conjugated PPE. An analysis of the electron-hole wave function reveals a sensitivity of energy and localization characteristics of the excited states to bends in the global conformation of the oligomer rather than to the relative of phenyl rings along the backbone.


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Authors and Affiliations

  1. 1.Department of Mathematics and Computer Science & Institute for Complex Molecular SystemsEindhoven University of TechnologyEindhovenThe Netherlands

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