飞秒时间分辨质谱和光电子影像对分子激发态动力学的研究

分子量子态的研究,特别是分子激发态演化过程的研究不仅可以了解分子量子态的基本特性和量子态之间的相互作用,而且可以了解化学反应过程和反应通道间的相互作用.飞秒时间分辨质谱和光电子影像是将飞秒抽运-探测分别与飞行时间质谱和光电子影像相结合的超快谱学方法,为实现分子内部量子态探测,研究分子量子态相互作用及超快动力学过程提供了强有力的工具,可以在飞秒时间尺度下研究单分子反应过程中的光物理或光化学机理.本文详细介绍了飞秒时间分辨质谱和光电子影像的技术原理,并结合本课题组的工作,展示了这两种方法在量子态探测及相互作用研究领域,特别是激发态电子退相、波包演化、能量转移、分子光解动力学以及分子激发态结构动力学研究中的广泛应用.最后,对该技术的发展前景以及进一步的研究工作和方向进行了展望.     

DMSO溶剂中All-trans-astaxanthin激发态的飞秒时间分辨光谱

基于飞秒时间分辨瞬态吸收和多元瞬态光栅光谱技术对全反式Astaxanthin(AXT)在DMSO溶剂中的超快激发态弛豫动力学进行了观测.结果表明,光激发后AXT/DMSO体系直接发生S_0→S_2跃迁,基态漂白对应光谱范围为420~550nm.由S_2→S_1的内转换过程发生的时间常数为120~160fs.S_1态激发态吸收对应的光谱范围为550~740nm,基态漂白恢复过程对应的是S_1→S_0的内转换过程,其时间尺度为4.50~5.50ps.     

酞菁锌分子激发态的超快内转移和振动弛豫

用飞秒时间分辨荧光亏蚀法研究了四特丁基酞菁（ＢｕＰｃ）、四特丁基酞菁锌（ＺｎＢｕＰｃ）和四丙氧基酞菁锌（ＺｎＰｒＰｃ）激发态的超快弛豫过程，用波长为３９８ｎｍ的超短脉冲激光激发分子，观察了Ｓ２态到Ｓ１态的内转换，其特征时间约为３０ｆｓ。在７９６ｎｍ先于３９８ｎｍ作用于样品分子时，观察到了荧光强度渐变的过程，通过分析认为这一过程反映了Ｓ１态的振动弛豫。通过对实验数据的拟合，得到了它们的振动弛豫特征时     

2-羟基吡啶S1态超快动力学

本文利用飞秒时间分辨的光电子成像技术研究了2-羟基吡啶分子在276.9∽250.0 nm波长范围的紫外光激发条件下S₁态的衰变动力学. 根据衰变动力学的泵浦波长相关性,提出了一种衰变机制. 在276.9 nm泵浦波长下,S₁态主要通过系间穿越到更低的三重态衰变. 在264.0 nm泵浦波长下,系间穿越到三重态和内转换到基态的通道同时存在. 在250.0 nm泵浦波长下,内转换到基态过程占据主导.     

团簇在超强超短脉冲激光场中的演化

利用低温脉冲气阀产生氘团簇束,在SILEX-Ⅰ激光装置上开展实验,研究氘团簇在超强超短脉冲激光场中的演化过程,获得了数十keV的高能氘离子,这些氘离子的能谱分布与库仑爆炸模型计算结果一致。实验结果表明,在一定的激光功率密度条件下,团簇的平均尺度决定了释放出高能离子的能谱分布。激光辐照团簇后,通过阈上电离部分电子逃逸团簇,随着初始电离电子屏蔽作用加强,碰撞电离变成了团簇的主要电离机制。     

团簇在超强超短脉冲激光场中的演化

 利用低温脉冲气阀产生氘团簇束,在SILEX-Ⅰ激光装置上开展实验,研究氘团簇在超强超短脉冲激光场中的演化过程,获得了数十keV的高能氘离子,这些氘离子的能谱分布与库仑爆炸模型计算结果一致。实验结果表明,在一定的激光功率密度条件下,团簇的平均尺度决定了释放出高能离子的能谱分布。激光辐照团簇后,通过阈上电离部分电子逃逸团簇,随着初始电离电子屏蔽作用加强,碰撞电离变成了团簇的主要电离机制。     

飞秒脉冲烧蚀单晶硅的超快动力学

利用基于Pump-probe系统的超快时间分辨阴影图的方法,研究了空气中飞秒激光烧蚀单晶硅的动力学过程。实验采用脉宽为50 fs、平均能量密度约35 J/cm2的单脉冲激光烧蚀单晶硅,获取飞秒激光烧蚀单晶硅过程中等离子体和冲击波的形成和发展过程的时间分辨阴影图。实验结果表明：飞秒激光烧蚀单晶硅导致其表面物质喷发的过程是不连续的,分为明显的两次喷发过程。这表明飞秒激光与单晶硅作用的过程中,在不同的时间段可能由不同的机制主导,在前期可能是多光子电离为主,在后期可能是由多光子效应和雪崩效应共同作用。研究还发现,延迟时间较长时,冲击波形状发生畸变。     

胆绿素二甲酯金属锌配合物超快激发态动力学研究

胆绿素(BV)及其二甲酯(BVE)是一种生物内源色素,他们在溶液中具有极弱的荧光,量子产率小于0.01%。然而,随着锌离子的加入,情况发生了变化. BVE-Zn²⁺配合物的荧光强度大大增强,荧光QY可提高到∽5%. 本文研究了BVE-Zn²⁺络合物在乙醇、正丙醇和二甲基亚砜溶液中的超快激发态动力学,以揭示其荧光增强的机理. 结果表明,BVE能与锌离子在溶液中形成1:1的稳定配合物,BVE分子结构在复合物中较为刚性,能量上更稳定. 利用皮秒时间分辨荧光光谱和飞秒瞬态吸收光谱技术,发现BVE-Zn²⁺配合物在二甲基亚砜中具有较小的非辐射速率常数,这是其高荧光量子产率关键原因.     

飞秒时间分辨拉曼光谱用于研究β-胡萝卜素单重激发态内转换和振动弛豫过程

搭建了飞秒时间分辨受激拉曼光谱(FSRS)装置,并用于研究全反式β-胡萝卜素单重电子激发态超快内转换和振动弛豫过程.基于三脉冲“抽运-探测”方案搭建的时间分辨受激拉曼光谱装置同时实现了150fs的时间分辨率和23.7cm^-1的光谱分辨率,光谱检测范围为300—4000cm^-1.对全反式β-胡萝卜素电子激发态的飞秒时间分辨拉曼光谱研究表明,β-胡萝卜素被激发到S₂态后,经由寿命约为0.3ps的中间态S_X态实 关键词： 飞秒时间分辨拉曼光谱 β-胡萝卜素 激发态内转换 振动弛豫     

飞秒时间分辨拉曼光谱用于研究β-胡萝卜素单重激发态内转换和振动弛豫过程

搭建了飞秒时间分辨受激拉曼光谱(FSRS)装置，并用于研究全反式β-胡萝卜素单重电子激发态超快内转换和振动弛豫过程.基于三脉冲“抽运-探测”方案搭建的时间分辨受激拉曼光谱装置同时实现了150fs的时间分辨率和23.7cm^-1的光谱分辨率，光谱检测范围为300—4000cm^-1.对全反式β-胡萝卜素电子激发态的飞秒时间分辨拉曼光谱研究表明，β-胡萝卜素被激发到S₂态后，经由寿命约为0.3ps的中间态S_X态实     

Control of the photoionization/photodissociation processes of cyclopentanone with trains of femtosecond laser pulses

A train of three equally spaced femtosecond laser pulses is employed to control the photoionization/photodissociation processes of cyclopentanone. With the increase of pulse separation, a strong modulation of product ion yield is observed. More than ten-fold changes of ion yield ratio between different products can be realized. The experimental observations further explain the compositions and formation pathways of peaks in the mass spectra. The controlling mechanisms are also discussed.     

Molecular dynamics simulation study of deep hole drilling in iron by ultrashort laser pulses

Classical molecular dynamics simulation technique is applied for investigation of the iron ablation by ultrashort laser pulses at conditions of deep hole for the first time. Laser pulse duration of 0.1 ps at wavelength of 800 nm is considered. The evolution of the ablated material in deep hole geometry differs completely from the free expansion regime as two major mechanisms are important for the final hole shape. The first one is the deposition of the ablated material on the walls, which narrows the hole at a certain height above its bottom. The second mechanism is related to ablation of the material from the walls (secondary ablation) caused by its interaction with the primary ablated particles. Properties of the secondary ablated particles in terms of the velocity and the angular distribution are obtained. The material removal efficiency is estimated for vacuum or in Ar environment conditions. In the latter case, the existence of well-defined vapor cloud having low center of the mass velocity is found. The processes observed affect significantly the material expulsion and can explain the decrease of the drilling rate with the hole depth increase, an effect observed experimentally.     

Particle sizing by ultrashort laser pulses – numerical simulation

This paper contains the results of our numerical investigations into particle sizing by analysis the time-dependent formation of the scattered light. We use an extended Mie theory for calculation the differences in time between the signals of reflection and higher order of refraction. The corresponding optical path lengths of light rays are computed by the principles of geometrical optics. By using a Debye series expansion it is possible to take into account single orders of scattered light. In detail we demonstrate the pulse-induced generation of scattered light for the refraction of first and second order as function of the detection angle.     

Numerical investigation of atomic dynamics in strong ultrashort laser pulses

The algorithms for the numerical solution of the stationary and nonstationary Schrödinger equations that allow the analysis of the dynamics of single-electron atoms in the presence of an external strong linearly polarized electromagnetic field in the dipole approximation are presented. Several examples of the simulation of atomic dynamics in the presence of high-intensity laser fields are considered to illustrate the possibilities of the proposed algorithms.     

X射线自由电子激光晶体学在结构生物学中的应用

X射线晶体学是获得生物大分子三维空间结构最主要的方法。基于X射线自由电子激光的晶体学——串行飞秒晶体学方法的出现,以其独特的优势为结构生物学研究提供了一种全新的研究手段。文章主要介绍了串行飞秒晶体学方法在结构生物学领域的应用及所取得的成果。这些成果表明该方法是在亚纳米空间尺度和飞秒时间尺度、在接近于自然状态下进行生物大分子静态和动态结构研究的强有力手段。     

超短激光脉冲

概述了超短激光脉冲技术的发展进程、研究进展及其在液态分子研究方面、超快现象等领域的应用。     

Microablation with ultrashort laser pulses

This paper reports the micromachining results of different materials (Al, Si, InP and fused silica) using a Ti : sapphire laser at the wavelength of 800 and 267 nm with variable pulse lengths in the range from 100 fs to 10 ps. The hole arrays with a diameter up to a few μm through microdrilling are presented. We discussed how an effective suppression of the thermal diffusion inside the ablated materials and an effective microablation could be realized. If the laser fluence is taken only slightly above the threshold, a hole array can be drilled with diameters even smaller than the wavelength of the laser. Some examples are presented in the paper.