Theoretical study of one- and two-photon absorption properties of pyrene derivatives

The geometrical structure, electronic structure, one-photon absorption (OPA) properties of pyrene and its derivatives have been theoretically studied by using density functional theory (DFT) method and Zerner's intermediate neglect of differential overlap (ZINDO) methods, and their two-photon absorption (TPA) properties are calculated by the ZINDO/sum-over-states method. The results show that introducing donor groups to pyrene molecule, increasing the number of donor groups, extending the conjugated length, or forming circular conjugated dimer can increase the oscillator strength (f) in the TPA process and ultimately result in extremely large TPA cross-sections and strong OPA around 400 nm of pyrene derivatives. All these results give us some basic principles to design pyrene derivatives with large TPA cross-sections. This shed light into the significance of the pyrene derivatives as promising fluorescent probes in biochemistry when they were linked to some special recognizing groups.