脉冲激光频域干涉技术在超快动力学物理中的应用

介绍了一种具有fs时间分辨力的超短脉冲激光频域干涉测试技术,详细论述了该技术的工作原理和系统构成,指出传输时间差和相位差是影响频域干涉条纹周期的主要因素。采用脉冲激光频域干涉仪测量了200 nm厚度铝膜在波长800 nm、单脉冲能量0.7 mJ、脉宽35 fs脉冲激光作用下的运动速度剖面。在单次飞秒脉冲激光作用下,铝膜自由面的运动速度峰值可达960 m/s,速度剖面的上升前沿小于5.77 ps,表明脉冲激光频域干涉技术可用于测量材料在超快脉冲激光作用下的冲击动力学参数。     

飞秒激光作用下质子产额及空间分布

在超短超强激光装置SILEX-Ⅰ上,利用HD810辐射变色膜在靶背法线方向测量了质子产额及空间分布。测量结果显示：光学密度与质子流量密切相关,光学密度越大,质子流量就越大;当C8H8厚度相同,Cu厚度增加时,质子产额随辐射变色膜的光学密度平均值减小而减小;当靶相同,激光功率密度越小时,光学密度平均值就越小,则质子产额也越小;实验中还得到了质子呈环状、成丝和圆盘状结构的空间分布,该空间分布的大小与激光焦斑大小无关。     

飞秒激光在透明介质中制备波导器件进展

飞秒激光脉冲通过非线性相互作用可以在透明介质内部诱导载流子的激发、弛豫和折射率改变,从而用于制备光波导器件。飞秒激光无法比拟的高度局域三维加工能力使其在有源和无源波导器件制备中被广泛研究。综述了飞秒激光在多种透明介质中诱导折射率改变的机理、波导器件制备的实验进展和波导性能优化技术,分析了其研究趋势和应用前景。     

Visible Light-Gated Organocatalysis Using a RuII-Photocage

The light-gated organocatalysis via the release of 4-N,N-dimethylaminopyridine (DMAP) by irradiation of the [Ru(bpy)₂(DMAP)₂]²⁺ complex with visible light was investigated. As model reaction the acetylation of benzyl alcohols with acetic anhydride was chosen. The pre-catalyst releases one DMAP molecule on irradiation at wavelengths longer than 455 nm. The photochemical process was characterized by steady-state irradiation and ultrafast transient absorption spectroscopy. The latter enabled the observation of the ³MLCT state and the spectral features of the penta-coordinated intermediate [Ru(bpy)₂(DMAP)]²⁺. The released DMAP catalyzes the acetylation of a wide range of benzyl alcohols with chemical yields of up to 99 %. Control experiments revealed unequivocally that it is the released DMAP which takes the role of the catalyst.     

Ultrafast photo-induced turning of magnetization and its relaxation dynamics in GaMnAs

We report that,by linearly polarized pumping of different wavelengths,Kerr transients appear at zero magnetic field only in the case when GaMnAs samples are initialized at 3 K by first applying a 0.8 Tesla field and then returning to zero field.We find that,instead of magnetization precession,the near-band gap excitation induces a coherent out-of-plane turning of magnetization,which shows very long relaxation dynamics with no precession.When photon energy increases,the peak value of the Kerr transient incre...     

噁嗪750激光染料分子在醇类溶剂中超快动力学研究

利用飞秒时间分辨荧光亏蚀光谱技术,研究了噁嗪750激光染料分子在典型的醇类溶剂中超快动力学过程.实验发现两个超快动力学过程:飞秒量级的快速弛豫过程和皮秒量级的慢速弛豫过程.快速弛豫过程来源于分子内振动能量再分配(IVR)和溶剂分子超快惯性弛豫动力学过程,而慢速弛豫过程对应于溶剂化的扩散分子弛豫动力学过程.实验结果表明慢速弛豫过程的时间常数随醇溶剂分子间氢键键能的增强而增大.     

Ultrafast Decay Dynamics of 2-Hydroxypyridine Excited to S1 Electronic State

The S\begin{document}$_1$\end{document} state decay dynamics of 2-hydroxypyridine following UV excitation at a wavelength range of 276.9\begin{document}$-$\end{document}250.0 nm is investigated using femtosecond time-resolved photoelectron imaging technique. Based on pump wavelength dependence of the decay dynamics, a refined decay picture is proposed. At pump wavelength of 276.9 nm, the S\begin{document}$_1$\end{document} state is depopulated through intersystem crossing to lower triplet state(s). At 264.0 nm, both intersystem crossing to lower triplet state(s) and internal conversion to the ground state are in operation. At 250.0 nm, internal conversion to the ground state becomes dominated.     

Photocatalytic Reduction of Nicotinamide Co-factor by Perylene Sensitized RhIII Complexes**

The ambitious goal of artificial photosynthesis is to develop active systems that mimic nature and use light to split water into hydrogen and oxygen. Intramolecular design concepts are particularly promising. Herein, we firstly present an intramolecular photocatalyst integrating a perylene-based light-harvesting moiety and a catalytic rhodium center ( Rh^IIIphenPer ). The excited-state dynamics were investigated by means of steady-state and time-resolved absorption and emission spectroscopy. The studies reveal that photoexcitation of Rh^IIIphenPer yields the formation of a charge-separated intermediate, namely Rh^IIphenPer ⋅ ⁺ , that results in a catalytically active species in the presence of protons.     

Radiation-Induced Oxidation Reactions of 2-Selenouracil in Aqueous Solutions: Comparison with Sulfur Analog of Uracil

One-electron oxidation of 2-selenouracil (2-SeU) by hydroxyl (^●OH) and azide (^●N₃) radicals leads to various primary reactive intermediates. Their optical absorption spectra and kinetic characteristics were studied by pulse radiolysis with UV-vis spectrophotometric and conductivity detection and by the density functional theory (DFT) method. The transient absorption spectra recorded in the reactions of ^●OH with 2-SeU are dominated by an absorption band with an λ_max = 440 nm, the intensity of which depends on the concentration of 2-SeU and pH. Based on the combination of conductometric and DFT studies, the transient absorption band observed both at low and high concentrations of 2-SeU was assigned to the dimeric 2c-3e Se-Se-bonded radical in neutral form (2^●). The dimeric radical (2^●) is formed in the reaction of a selenyl-type radical (6^●) with 2-SeU, and both radicals are in equilibrium with K_eq = 1.3 × 10⁴ M⁻¹ at pH 4 (below the pK_a of 2-SeU). Similar equilibrium with K_eq = 4.4 × 10³ M⁻¹ was determined for pH 10 (above the pK_a of 2-SeU), which admittedly involves the same radical (6^●) but with a dimeric 2c-3e Se-Se bonded radical in anionic form (2^●−). In turn, at the lowest concentration of 2-SeU (0.05 mM) and pH 10, the transient absorption spectrum is dominated by an absorption band with an λ_max = 390 nm, which was assigned to the ^●OH adduct to the double bond at C5 carbon atom (3^●) based on DFT calculations. Similar spectral and kinetic features were also observed during the ^●N₃-induced oxidation of 2-SeU. In principle, our results mostly revealed similarities in one-electron oxidation pathways of 2-SeU and 2-thiouracil (2-TU). The major difference concerns the stability of dimeric radicals with a 2c-3e chalcogen-chalcogen bond in favor of 2-SeU.     

Ultrafast Excited State Relaxation Dynamics of New Fuchsine- a Triphenylmethane Derivative Dye

An all-inclusive investigation of the ultrafast excited state relaxation dynamics of a triphenylmethane derivative molecule, New Fuchsine (NF), using a combined approach of density functional theory (DFT), femtosecond transient absorption spectroscopy (fs-TAS), and photoluminescence spectroscopy is presented in this work. The DFT calculations confirmed the formation of twisted molecular structure in the excited state of NF in ethanol solution with bond rotation of ≈86°. TAS measurements of NF solution exhibited ultrafast ground state-recovery pathway via a conical intersection confirming an ultrafast structural reorientation. On the contrary, TAS measurements of NF thin-film exhibited a longer excited-state lifetime suggesting a hindered molecular twisted state formed as an intermediate step. Photophysical kinetic models are proposed to globally fit the fs-TAS data establishing the twisted intramolecular charge transfer (TICT) state mediated ground state recovery for NF in solution and thin film, respectively. Temperature-dependent photoluminescence study of NF film provided a clear insight into the effect of rotational motion of phenyl rings in NF molecules over the TICT mediated emission.