Abstract
Two-photon absorption (TPA) properties of noncentrosymmetric pi-conjugated stilbenoid molecules with D-pi-A structures, TPA spectra of which have been reported [L. Antonov et al., Phys. Chem. Chem. Phys. 5, 1193 (2003)], have been investigated theoretically by ab initio molecular orbital methods. The difference in the observed one-photon absorption and TPA spectra among compounds with the same donor (D) and acceptor (A) units is well reproduced by the present calculations, although the calculated excitation energies are overestimated by the configuration interaction with single excitation method used. It was found that the spectral differences among the compounds were mainly due to the deviation from the planar structure by intramolecular rotation around the N[Single Bond]C (phenyl) bond of the N-benzilideneanilines having the C[Double Bond]N linkage as the central pi bridge. Substitution of the end donor or acceptor groups with weaker ones leads to a decrease in the TPA intensity of the lowest pi-pi(*) TPA states, resulting mainly from the decrease in the dipole moment of the excited states. The total TPA cross section spectra have been separated into contributions of the dipolar term, which appear only in noncentrosymmetric systems, and the three-state term, which appear in any systems irrespective of symmetry. The dipolar term predominates only for the lowest pi-pi(*) state, while for the higher excited states the three-state terms become predominant. An analysis employing the index R(f) defined with the transition polarizability shows that the TPA properties of the higher excited states are well described by the three-state approximation mediated by the lowest pi-pi(*) state. The differences found between the centrosymmetric and dipolar molecules in the enhancement mechanism of the TPA intensity by substituting the end groups with strong donors are discussed by comparison with the TPA properties of azobenzenes symmetrically substituted with the same donors.
Published Version
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