We determine the dispersion of the third-order polarizability of small donor-acceptor substituted organic molecules using wavelength-dependent degenerate four-wave mixing experiments in solutions with varying concentrations. We find that donor-acceptor–substituted molecules that are characterized by extremely efficient off-resonant nonlinearities also have a correspondingly high two-photon absorption cross section. The width and shape of the first two-photon resonance for these noncentrosymmetric molecules follows what is expected from their longest wavelength absorption peak, and the observed two-photon absorption cross sections are record high when compared to the available literature data, the size of the molecule, and the fundamental limit for two-photon absorption to the lowest excited state, which is essentially determined by the number of conjugated electrons and the excited-state energies. The two-photon absorption of the smallest molecule, which only has 16 electrons in its conjugated system, is one order of magnitude larger than for the molecule called AF-50, a reference molecule for two-photon absorption [O.-K. Kim et al., Chem. Mater. 12, 284 (2000)].

• Received 31 December 2014

DOI:https://doi.org/10.1103/PhysRevA.91.043818