Effects of aggregation on the structures and excited-state absorption for zinc phthalocyanine

In the present paper, the aggregated structures of zinc phthalocyanine (ZnPc) have been investigated by considering its dimers and trimers. Based on the density functional theory calculations, two stable conformations are obtained for the ZnPc dimer and trimer, respectively. The IGMH (independent gradient model based on the Hirshfeld partition of molecular density) analysis reveals that the π-π interaction between the ZnPc molecules causes the aggregation. Normally, stacked structures with a slight displacement are favorable for aggregation. In addition, the planar structure of the ZnPc monomer is largely maintained in the aggregated conformations. For the presently obtained structures, the first singlet excited state absorption (ESA) spectra of these aggregated conformations of ZnPc were calculated based on the linear-response time-dependent density functional theory (LR-TDDFT), which has been well applied by our group. The results of the excited state absorption spectra reveal that the aggregation causes the ESA band to blue shift compared to the ZnPc monomer. By using the conventional description of the interaction between monomer transition dipoles, this blue shift is elucidated by the side-by-side transition dipole moments in the constituted monomers. The present results for the ESA combined with the previously reported results for ground state absorption (GSA) will provide guidelines to tune the window of the optical-limiting effect for the ZnPc based materials.