飞秒脉冲激光啁啾对4,4’-二(二正丁胺基)二苯乙烯的光限幅及动态双光子吸收的影响(英文)

通过采用预估矫正的时域有限差分方法(FDTD)数值求解Maxwell-Bloch方程,研究飞秒啁啾脉冲激光在4,4’-二(二正丁胺基)二苯乙烯(BDBAS)分子介质中的光限幅行为(OL)和动态双光子吸收(TPA)截面.计算表明啁啾率的符号和大小都对频谱演化和光限幅行为产生影响.啁啾率的符号决定频移的方向:正啁啾对应频谱蓝移,负啁啾对应频谱红移.随着啁啾率绝对值的增大,频移更加明显,光限幅窗口变窄,同时出射光强饱和值变大.有趣的是,当负啁啾降低到一定值(-0.025/fs2)时,出现自感应透明(SIT)现象.另外,动态双光子吸收截面在考虑啁啾效应的情况下减小.本研究提供了一种控制非线性光学吸收的方法.     

Responsive mechanism of 2-(2'-hydroxyphenyl)benzoxazole-based two-photon fluorescent probes for zinc and hydroxide ions

Response theory is used to investigate one- and two-photon absorption(TPA) as well as the emission properties of a series of potential zinc ion and pH sensitive materials containing 2-(2’-hydroxyphenyl)benzoxazole(HPBO) end groups.Special emphasis is placed on the evolution of their optical properties upon combining with zinc ions or deprotonation.Our calculated results indicate that upon combining with zinc ions or deprotonation,these HPBO derivatives show drastic changes in their one-photon absorption(OPA),emission,and TPA properties.Moreover,the mechanisms of the probes are analyzed and found to be an intramolecular charge transfer.These compounds are thus proved to be excellent candidates for two-photon fluorescent zinc and pH probes.     

侧基对π-π耦合双分子结电输运性质的影响

从第一性原理出发，利用杂化密度泛函理论，结合弹性散射格林函数方法，我们研究了侧基对OPE（Oligophenyleneethynylene）双分子结电输运性质以及两分子间的π-π耦合作用的影响。研究表明，苯环上的侧基影响了两分子间的π-π耦合强度。当侧基为氧甲基时，侧基提高了分子间的π-π耦合作用，促进了分子间电荷的传输。当侧基为叔丁基时，侧基降低了π-π耦合作用，不利于分子间电荷的传输。理论计算结果解释了实验结果。     

One- and two-photon absorption properties of two metalloporphyrin complexes

The linear and nonlinear optical properties of two metalloporphyrin complexes formed by the complementary coordination of central zinc or magnesium ions to the ligand 5, 10, 15-tri-(p-tolyl)-20-phenylethynylporphyrin are theoretically investigated by using the analytic response theory at the density functional theory level. The results indicate that the studied complexes present more symmetric geometry structures than the ligand. The charge-transfer states of the two complexes in the lower energy region are all almost degenerate but those of the ligand are well separated. The ratio of the two-photon absorption cross sections of the ligand, zinc-porphyrin and magnesium-porphyrin complexes is 1.0:1.5:1.8, demonstrating that the two-photon absorption capability can be greatly increased when the ligand is coordinated with a metal ion. Moreover, several physical micro-mechanisms including electron transitions and intramolecular charge-transfer processes are discussed to explore the differences in optical property between the ligand and two complexes.     

Effect of Lorentz local field correction on propagation of ultrashort laser pulse in one-dimensional para-nitroaniline (PNA) molecules

This paper investigates the effect of Lorentz local field correction (LFC) on the propagation of ultrashort laser pulses in a para-nitroaniline molecular medium under resonant and nonresonant conditions by solving numerically the full-wave Maxwell-Bloch equations beyond slowly-varying envelope approximation and rotating-wave approximation. The effect of the LFC is considerably obvious when pulses with large areas propagate in the dense molecular medium. In the case of resonance,the group velocity of the sub-pulses split from the incident pulse along propagation is severely decreased by the LFC,especially for the latest sub-pulse. However,in the case of nonresonance,the influence of the LFC on the temporal evolution of the pulse is less obvious and lacks homogeneity with an increase in incident pulse area,propagation distance and molecular density.     

烯/炔基有机共轭分子双光子吸收特性的理论研究-溶剂效应

The present work concerns the study of solvent effects on the geometrical structures, as well as one- and two-photon absorption (TPA) processes, for two series of alkyne and alkene π-bridging molecules, within the framework of the polarization continuum model. Particular emphasis was put on the characterization of solvent effects on the molecular geometrical structures and geometric distortion, which were measured by the bond-length-alternation parameter. The π centres in the compounds are seen to play a decisive role in increasing the TPA cross section and nonlinear optical properties. All studied molecules have relatively strong TPA characteristics, while the alkyne π-bridging ones yield larger TPA cross sections.     

Carrier--envelope phase effects for a dipolar molecule interacting with ultrashort laser pulse

In this paper the phase-dependent features of ultrashort laser pulse resonant propagation in a two-level dipolar molecule are demonstrated by solving full Maxwell--Bloch equations. The electronic properties of dipolar molecule 4-trans-[p-(N, N-Di-n-butylamino)-p -stilbenylvinyl] pyridine (DBASVP) molecule, one-dimensional asymmetric organic molecule, is calculated by density functional theory at \textit{ab initio} level. The numerical results show that the carrier propagation and the spectrum evolution of the pulse are sensitive to its initial phase and the phase sensitivity is more obvious for larger area pulse. The phase-dependent feature is more evident in dipolar molecule because the permanent dipole moment makes the nonlinear effects stronger.     

不同构型罗丹明分子拉曼光谱的密度泛函理论研究

利用密度泛函理论研究了罗丹明6G、罗丹明123和罗丹明B分子的拉曼光谱. BP86泛函计算的罗丹明系列分子的阳离子在气相中的拉曼光谱与相应的分子在水溶液中的实验光谱符合很好. 结果显示氯离子以及氢键的引入对罗丹明B分子的拉曼光谱有较明显的影响,该影响可以部分地解释罗丹明B分子在水溶液中和在金表面上拉曼光谱的不同. 精确描述罗丹明分子在金属表面的表面增强拉曼光谱,需要考虑由界面相互作用而导致的变化.     

D-A型二噻吩并磷杂茂衍生物分子的双光子吸收性质

在密度泛函理论理论水平上,采用响应理论方法计算了一系列2,6-donor-acceptor二噻吩并磷杂茂衍生物分子的单、双光子吸收性质.理论计算结果表明该系列分子都具有较大的双光子吸收截面,并且分子中心的磷原子无论被氧化还是金属配合,其双光子吸收截面几乎保持不变.此外,还考虑了溶剂效应对分子光学性质的影响,研究表明分子能级发生了溶剂化蓝移,并且分子的单光子和双光子吸收性质随着溶剂极性表现出非单调变化.     

飞秒激光脉冲在三能级有机分子介质中传播时的频谱分析

通过采用预估校正的时域有限差分法求解麦克斯韦-布洛赫方程,我们研究了飞秒激光脉冲在三能级有机分子(4,4-二甲氨基二苯乙烯分子)介质中传播时脉冲的频谱演化情况.在单光子共振情况下,即入射脉冲频率等于1、2能级之间的共振频率,对大面积入射脉冲,由于强的二次激发的作用,电场频谱中出现了在ω32附近振荡的频率成分,ω32是2、3能级之间的共振频率,说明对大面积入射脉冲二能级模型已经失效,需要采用多能级模型来描述分子介质.在双光子共振情况下,即入射脉冲频率等于1、3能级之间的共振频率的一半,由于介质中放大的自发辐射和四波混频的作用,部分入射脉冲能量转化为高频和低频电场成分的能量,分子介质表现出了很强的光功率限幅特性.