Evidences of long lived cages in functionalized polymers: Effects on chromophore dynamic and spectroscopic properties

The formation of long-lived cages in a functionalized polymer is evidenced through an integrated computational approach. The investigated material is described with a purposely refined force field and long lasting simulations are used to sample the configurational space of the complex. The resulting virtual scenario is validated by comparing calculated and experimental spectra. The deeper insight offered by the computational procedure has lead to the identification of flexible cage like structures of the polymer bundle, that evolve very slowly, readapting their shape to the thermal movements of the probe, hence affecting the broadening of the electronic spectra. (C) 2014 Elsevier B.V. All rights reserved.