Zhao Yang, Ren Ai-Min, Feng Ji-Kang, Sun Chia-Chung
State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People's Republic of China.
J Chem Phys. 2008 Jul 7;129(1):014301. doi: 10.1063/1.2938374.
The geometrical structure, electronic structure, one-photon absorption (OPA) and two-photon absorption (TPA) properties of the perylene tetracarboxylic derivatives (PTCDs) were studied theoretically by using density functional theory (DFT) and Zerner's intermediate neglect of differential overlap (ZINDO) methods. The results revealed that increasing the number of naphthalene nucleus, extending the conjugated length on long axis, increasing the strength of donor group on lateral side, decreasing the DeltaE(H-L) (energy gap between the highest occupied orbital and the lowest unoccupied orbital) and keeping the conjugation effect and inductive effect along the same molecular axis are the efficient ways to enlarge TPA cross section of PTCDs compounds. The results that PTCDs compounds exhibited extremely large TPA cross section of around 800-1100 nm (near infrared region) shed light into the significance of the PTCDs compounds for applications in TPA labeling materials in vivo.
采用密度泛函理论（DFT）和Zerner的间略微分重叠方法（ZINDO），对苝四羧酸衍生物（PTCDs）的几何结构、电子结构、单光子吸收（OPA）和双光子吸收（TPA）性质进行了理论研究。结果表明，增加萘核的数量、延长长轴上的共轭长度、增强侧链供体基团的强度、减小ΔE（H-L）（最高占据轨道与最低未占据轨道之间的能隙）以及保持沿同一分子轴的共轭效应和诱导效应，是增大PTCDs化合物TPA截面的有效方法。PTCDs化合物在800-1100nm左右（近红外区域）表现出极大的TPA截面，这一结果为PTCDs化合物在体内TPA标记材料中的应用意义提供了线索。
