Time-dependent hybrid density functional theory in combination with polarized continuum model is applied to study the solvent effects on the geometrical and electronic structures as well as one- and two-photon absorpt...Time-dependent hybrid density functional theory in combination with polarized continuum model is applied to study the solvent effects on the geometrical and electronic structures as well as one- and two-photon absorption processes, of a newly synthesized asymmetrical charge-transfer organic molecule bis-（4-bromo-phenyl）-[4-（2-pyridin-4-yl-vinyl）phenyl]-amine （BPYPA）. There exist two charge-transfer states for the compound in visible region. The two-photon absorption cross section calculated by a three-state model and solvatochromic shift of the charge-transfer states are found to be solvent-dependent, where a nonmonotonic behaviour with respect to the polarity of the solvents is observed. The numerical results show that the organic molecule exhibits a rather large two-photon absorption cross section as compared with the compound 4-trans-[p-（N, N-Di-n-butylamino）-p-stilbenyl vinyl] pyridine （DBASVP） reported previously, and is predicted to be a good two-photon polymerization initiator. The hydrogen-bond effect is analysed. The computational results are in good agreement with the measurements.展开更多
On the level of the time-dependent hybrid density functional theory, the one- and two-photon absorption properties of a series of symmetric 4-bis{2-[4-（2-aryl） phenyl]vinyl）-2,5-bisdialkoxybenzenes are studied resp...On the level of the time-dependent hybrid density functional theory, the one- and two-photon absorption properties of a series of symmetric 4-bis{2-[4-（2-aryl） phenyl]vinyl）-2,5-bisdialkoxybenzenes are studied respectively utilizing the analytic response theory and the few-state model methods. The calculated results show that the planarity of the geometrical structure plays a great role in enhancing the linear and nonlinear optical abilities of the molecule. However the effect of the length of the chain linked to the π-centre on the optical property is very little. For the investigated compounds, the A-π-A type charge-transfer molecules display more superior one- and two-photon absorption characteristics than the D-π-D type ones. Furthermore, the two-photon absorption results by use of few-state model are generally consistent with those by analytic response theory, demonstrating the reliability of the few-state model for evaluating the two-photon absorption cross section. The numerical simulations are in good agreement in tendency with the available experimental measurements.展开更多
基金Project supported by the National Natural Science Foundation of China （Grant No 10274044） and Shandong Natural Science Foundation （Grant No Y2004A08）.
文摘Time-dependent hybrid density functional theory in combination with polarized continuum model is applied to study the solvent effects on the geometrical and electronic structures as well as one- and two-photon absorption processes, of a newly synthesized asymmetrical charge-transfer organic molecule bis-（4-bromo-phenyl）-[4-（2-pyridin-4-yl-vinyl）phenyl]-amine （BPYPA）. There exist two charge-transfer states for the compound in visible region. The two-photon absorption cross section calculated by a three-state model and solvatochromic shift of the charge-transfer states are found to be solvent-dependent, where a nonmonotonic behaviour with respect to the polarity of the solvents is observed. The numerical results show that the organic molecule exhibits a rather large two-photon absorption cross section as compared with the compound 4-trans-[p-（N, N-Di-n-butylamino）-p-stilbenyl vinyl] pyridine （DBASVP） reported previously, and is predicted to be a good two-photon polymerization initiator. The hydrogen-bond effect is analysed. The computational results are in good agreement with the measurements.
基金Project supported by the State Key Development Program for Basic Research of China(Grant No.2006CB806000)the Open Fund of the State Key Laboratory of High Field Laser Physics(Shanghai Institute of Optics and Fine Mechanics),Higher Educational Science and Technology Program of Shandong Province(Grant No.J09LA13)
文摘On the level of the time-dependent hybrid density functional theory, the one- and two-photon absorption properties of a series of symmetric 4-bis{2-[4-（2-aryl） phenyl]vinyl）-2,5-bisdialkoxybenzenes are studied respectively utilizing the analytic response theory and the few-state model methods. The calculated results show that the planarity of the geometrical structure plays a great role in enhancing the linear and nonlinear optical abilities of the molecule. However the effect of the length of the chain linked to the π-centre on the optical property is very little. For the investigated compounds, the A-π-A type charge-transfer molecules display more superior one- and two-photon absorption characteristics than the D-π-D type ones. Furthermore, the two-photon absorption results by use of few-state model are generally consistent with those by analytic response theory, demonstrating the reliability of the few-state model for evaluating the two-photon absorption cross section. The numerical simulations are in good agreement in tendency with the available experimental measurements.
