Theoretical Study on One- and Two-Photon Absorption Properties of π-Stacked Multimer Models of Phenalenyl Radicals

Effects of the number of monomers (N) on the two-photon absorption (TPA) properties of pi-stacked multimer models consisting of phenalenyl radicals were investigated theoretically. We conducted spectral simulations for the pi-stacked N-mer models (N = 2, 4, and 6) with different stacking distances (d1) and their alternation patterns (d2/d1). Excitation energies and transition dipole moments were calculated at the extended multi-configurational quasi-degenerate second-order perturbation theory (XMC-QDPT2) level based on the complete active space self-consistent field (CASSCF) wavefunctions with the active space orbitals constructed from the singly occupied molecular orbitals (SOMOs) of monomers. The TPA cross-section value per dimer unit at the first peak, originating from the electronic transition along the stacking direction, was predicted to increase significantly as the d2/d1 approaches one, as the d1 decreases, and as the N increases from 2 to 6. These tendencies are similar to the calculation results for the static hyperpolarizabilities.