ELECTRONIC STRUCTURES, EXCITED SPECTRA, AND NONLINEAR OPTICAL PROPERTIES OF N-METHYL–FULLEROPYRROLIDINE–OLIGOANILINE DYADS NMPC60–ANn (n = 1–5): QUANTUM CHEMISTRY STUDY

Abstract

The geometrical and electronic structures of a series of dyads NMPC60–AN n (n = 1–5) were investigated at B3LYP/6-31G* level. Then, the excited states were calculated at TDB3LYP/3-21G* level to investigate the photophysical properties. The third-order polarizabilities of degenerate four-wave mixing (DFWM), electric-field-induced second-harmonic generation (EFISHG), and third-harmonic generation (THG) were calculated in combination with the sum-over-states (SOS) method. The obtained absorption spectra show a remarkable red shift. The average value of third-order polarizabilities 〈γ〉 away from the resonant region increases with n for NMPC60–AN n. The charge transfers from the oligoanilines to C60 cage make the main contribution to the large third-order polarizabilities of this series of compounds. It is found that 〈γ〉 can be expressed as a function of the chain length of linked oligoaniline and 11.74 × 10-34 esu is the upper limit after n = 7 for NMPC60–AN n in the static state.