摘要
Based on the equilibrium structures from quantum mechanics AM1 method, employing INDO/CI method and the sum-over-state （SOS） formula, the one-photon absorption （OPA） and two-photon absorption （TPA） properties as well as the second hyperpolarizabilities were discussed in detail for a kind of PPV derivative poly 2-（9-phenylanthracen-10-yl）-1,4-phenylenevinylene （P1）. The results indicate that the two-photon cross section （3） increases with the increasing of the number of repeating segment （n）, however only a slight increase corresponds to the increasing of molecular weight when the repeating unit number arrives at a certain number. From this point of view, the TPA cross section values of P1 were extrapolated through the linear fit of 3 value vs. 1/n. The δ value of P1 is as high as 181 GM （1 GM=10^-50 cm^4·s·photon^-1）. Concerning the influence of pendent group and extension of π-conjugation on 3 values, another four oligomers P2, PPV, P1-1, and P2-1 were investigated for comparison. The calculation results reveal that the position and property of pendent group have great influence on the OPA and TPA properties. A most crucial role for relatively larger 3 value was played by the extension of π-conjugation.
Based on the equilibrium structures from quantum mechanics AM1 method, employing INDO/CI method and the sum-over-state （SOS） formula, the one-photon absorption （OPA） and two-photon absorption （TPA） properties as well as the second hyperpolarizabilities were discussed in detail for a kind of PPV derivative poly 2-（9-phenylanthracen-10-yl）-1,4-phenylenevinylene （P1）. The results indicate that the two-photon cross section （3） increases with the increasing of the number of repeating segment （n）, however only a slight increase corresponds to the increasing of molecular weight when the repeating unit number arrives at a certain number. From this point of view, the TPA cross section values of P1 were extrapolated through the linear fit of 3 value vs. 1/n. The δ value of P1 is as high as 181 GM （1 GM=10^-50 cm^4·s·photon^-1）. Concerning the influence of pendent group and extension of π-conjugation on 3 values, another four oligomers P2, PPV, P1-1, and P2-1 were investigated for comparison. The calculation results reveal that the position and property of pendent group have great influence on the OPA and TPA properties. A most crucial role for relatively larger 3 value was played by the extension of π-conjugation.
基金
Project supported by the National Natural Science Foundation of China （No. 20373009）, the Specialized Research Fund for the Doctoral Program in Higher Education Institutions of the Ministry of Education of China （No. 20030183063） and Science Foundation for Young Teachers of Northeast Normal University （No. 20060311）.
