π-conjugated dendrimers are molecular examples of tree-like structures known in physics as Bethe lattices. Electronic excitations in these systems can be spatially delocalized or localized depending on the branching topology. Without a priori knowledge of the localization pattern, understanding photoexcitation dynamics reflected in experimental optical spectra is difficult. ‘Supramolecular’-like quantum-chemical calculations quickly become intractable as the molecular size increases. Here we develop a reduced exciton-scattering (ES) model, which attributes excited states to standing waves in quasi-one-dimensional structures, assuming a quasiparticle picture of optical excitations. Direct quantum-chemical calculations of branched phenylacetylene chromophores are used to verify our model and to derive relevant parameters. Complex and non-trivial delocalization patterns of photoexcitations throughout the entire molecular tree can then be universally characterized and understood using the proposed ES method, completely bypassing ‘supramolecular’ calculations. This allows accurate modelling of excited-state dynamics in arbitrary branched structures.
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V.Y.C. acknowledges the support through the start-up funds from WSU. The research at LANL is supported by the Center for Integrated Nanotechnology (CINT), the Center for Nonlinear Studies (CNLS) and the OBES program of the US Department of Energy. This support is gratefully acknowledged.
The authors declare no competing financial interests.
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Wu, C., Malinin, S., Tretiak, S. et al. Exciton scattering and localization in branched dendrimeric structures. Nature Phys 2, 631–635 (2006). https://doi.org/10.1038/nphys389
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