Computational Study of the Structure, Dynamics, and Photophysical Properties of Conjugated Polymers and Oligomers under Nanoscale Confinement

Journal Article · Fri Apr 01 04:00:00 EST 2005 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI:https://doi.org/10.1021/jp0446534· OSTI ID:1564614

Sumpter, Bobby G.; Kumar, Pradeep; Mehta, Adosh; Barnes, Michael D.; Shelton, William A.; Harrison, Robert J.

Computational simulations were used to investigate the dynamics and resulting structures of several para-phenylenevinylene (PPV) based polymers and oligomers (PPV, 2-methoxy-5-(2‘-ethyl-hexyloxy)-p-phenylenevinylene → MEH–PPV and 2,5,2‘,5‘-tetrahexyloxy-7,8‘-dicyano-p-phenylenevinylene → CN–PPV). The results show how the morphology and structure are controlled to a large extent by the nature of the solute–solvent interactions in the initial solution-phase preparation. Secondary structural organization is induced by using the solution-phase structures to generate solvent-free single molecule nanoparticles. Isolation of these single molecule nanostructures from microdroplets of dilute solution results in the formation of electrostatically oriented nanostructures at a glass surface. Our structural modeling suggests that these oriented nanostructures consist of folded PPV conjugated segments with folds occurring at tetrahedral defects (sp³ C–C bonds) within the polymer chain. This picture is supported by detailed experimental fluorescence and scanning probe microscopy studies. We also present results from a fully quantum theoretical treatment of these systems which support the general conclusion of structure-mediated photophysical properties.

• Research Organization: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF), Oak Ridge, TN (United States)
• Sponsoring Organization: USDOE Office of Science (SC)
• OSTI ID: 1564614
• Journal Information: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Journal Name: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry Journal Issue: 16 Vol. 109; ISSN 1520-6106
• Publisher: American Chemical Society
• Country of Publication: United States
• Language: English

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