The aggregation effects on the two-photon absorption properties of para-nitroaniline polymers by hydrogen-bond interactions

This paper has theoretically designed a series of aggregate polymers on the basis of several para-nitroaniline monomers by hydrogen-bond interactions. At the level of time-dependent hybrid density functional theory, it has optimized their geometrical structures and studied their two-photon absorption (TPA) properties by using analytical response theory. The calculated results exhibit that the aggregation effects not only bring out the considerable red shift of the excited energies but also greatly enhance the TPA intensities of the aggregate polymers in comparison with the para-nitroaniline monomer. The aggregate configurations also have an important influence on the TPA abilities of the polymers; the trimer has the largest TPA cross section. The electron transitions between the molecular orbits involving the strong TPA excitations of the trimer are depicted to illuminate the relationship between the intermolecular charge transfer and the TPA property. (classical areas of phenomenology)