Time-wavelength two-dimensional femtosecond fluorescence imaging

We report a new femtosecond time-resolved fluorescence spectrometer that enables us to observe fluorescence intensity as a time-wavelength two-dimensional image in a single measurement. This method utilizes a time-to-space conversion technique and fluorescence sum-frequency mixing with a femtosecond gate pulse. It provides a fluorescence image covering temporal and spectral spans of approximately 2 ps and approximately 60 nm, respectively. Calibration of the time and intensity axes of the image is made by use of a long-lived dye fluorescence. The two-dimensional fluorescence image of beta-carotene obtained demonstrates the high potential of this method for quantitative studies of ultrafast excited-state dynamics.     

A Surface Femtosecond Two-Photon Photoemission Spectrometer for Excited Electron Dynamics and Time-Dependent Photochemical Kinetics

搭建了一套研究金属和金属氧化物表面的超快激发态电子动力学和光化学动力学的飞秒双光子光电子能谱仪. 该装置将半球形电子能量分析仪和成像技术相结合,同时测量光电子的能量和角度分布.通过Mach-Zehnder干涉仪测量时间分辨的双光子光电子能谱获得超快激发电子态的动力学信息. 这一功能在Cu(111)上得到了证实. 另外还发展了一个通过实时测量双光子光电子能谱来研究表面光化学的方法,并成功应用到CH₃CH₂OH/TiO₂(110)体系. 研究表明,只有将两种方法结合起来才能正确地研究光诱导的表面激发共振的动力学.     

Sub‐picosecond Raman spectrometer for time‐resolved studies of structural dynamics in heme proteins

We describe a pump–probe Raman spectrometer based on a femtosecond Ti:sapphire laser, an optical parametric generator and two optical parametric amplifiers for time‐resolved studies, with emphasis on the structural dynamics in heme proteins. The system provides a 100‐fs pump pulse tunable in the range 500–600 nm and a transform‐limited sub‐picosecond probe pulse tunable in the range 390–450 nm. The spectrometer has spectral (25 cm⁻¹) and temporal (∼0.7 ps) resolutions which constitute an effective compromise for identifying transient heme protein species and for following their structural evolution by spontaneous Raman scattering in the time range 0.5 ps to 2 ns. This apparatus was applied to time‐resolved studies of a broad range of heme proteins, monitoring the primary dynamics of photoinduced heme coordination state and structural changes, its interaction with protein side‐chains and diatomic gaseous ligands, as well as heme vibrational cooling. The treatment of transient Raman spectra is described in detail, and the advantages and shortcomings of spontaneous resonance Raman spectroscopy for ultrafast heme proteins studies are discussed. We demonstrate the efficiency of the constructed spectrometer by measuring Raman spectra in the sub‐picosecond and picosecond time ranges for the oxygen‐storage heme protein myoglobin and for the oxygen‐sensor heme protein FixLH in interaction with the diatomic gaseous ligands CO, NO, and O₂. Copyright © 2010 John Wiley & Sons, Ltd.     

Interferometric characterization of ultrashort deep ultraviolet pulses using a multiphoton ionization mass spectrometer

The temporal characterization of a femtosecond laser pulse in the deep ultraviolet region using an interferometric autocorrelation scheme is demonstrated. Two-photon ionization of a molecule in a time-of-flight mass spectrometer was used as a nonlinear detector to obtain an autocorrelation trace. This setup proved useful in not only providing a temporal characterization of a pulse but also investigating the ultrafast dynamics of photochemical processes.     

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.     

Femtosecond laser user facility for application research on ultrafast science

The advent of chirped-pulse amplification(CPA) has greatly advanced the field of ultrafast and ultra-intense laser technology. CPA has become an indispensable platform for multidisciplinary research, such as physics, chemistry, life sciences, and precision metrology. The femtosecond laser facility at the Synergic Extreme Condition User Facility(SECUF)is a comprehensive experimental platform with an advanced femtosecond laser source for ultrafast scientific research. It will provide an ultrafast scientific research system having a few-cycle pulse duration, wide spectral range, high energy, and high repetition rate for multipurpose applications.     

Generation of tunable octave-spanning mid-infrared pulses by filamentation in gas media

The continued development of femtosecond mid-infrared (IR) sources with ultrabroad spectral width is critical for probing and controlling complex molecular structural dynamics on an ultrafast timescale. We report on a sub-20 fs, coherent mid-IR source with an octave-spanning spectral bandwidth (>2000 cm(-1)) tunable from 2-8 micrometers (37.5-150 THz), with energy >0.4 μJ/pulse at 1 kHz. The mid-IR pulses are generated by four-wave mixing during the filamentation of intense 800 nm and 400 nm pulses in various gas media. Spectral tunability is achieved by the choice of gas, pressure and input 800 nm pulse energy.     

Femtosecond stimulated Raman spectroscopy

Advances in the field of Femtosecond Stimulated Raman Spectroscopy (FSRS), a new time‐resolved structural technique that provides complete vibrational spectra on the ultrafast timescale, are reviewed. When coupled with a femtosecond optical trigger, the time evolution of a reacting species can be monitored with unprecedented <25 femtosecond temporal and 5 cm^‐1 spectral resolution. New technological and theoretical advances including the development of tunable FSRS and a background‐free FSRS format are discussed. The most recent experimental studies focus on ultrafast reaction dynamics in electronically excited states: isomerization in cyanobacterial phytochrome, ultrafast spin flipping in a solar cell sensitizer, and excited state proton transfer in green fluorescent protein. The use of FSRS to directly map multidimensional reactive potential energy surfaces and to probe the mechanism of reactive internal conversion is prospectively discussed.     

基于阿秒XUV-飞秒IR泵浦-探测的冷靶反冲离子动量成像谱仪

利用多道可见光谱探测系统测量了Hα、CⅢ(464.7nm)和OⅡ(441.5nnm)谱线的时间行为,得出了碳、氢和氧元素的入射通量。在简化模型下算出了氧碳间的化学溅射率,结果表明HT-6M托卡马克边界杂质产生机制主要是氢氧间的化学溅射和氧碳间的化学溅射,因此控制氧杂质尤其重要。     

Laser-induced fluorescence detection of hydroxyl (OH) radical by femtosecond excitation

The development of a laser-induced fluorescence detection scheme for probing combustion-relevant species using a high-repetition-rate ultrafast laser is described. A femtosecond laser system with a 1 kHz repetition rate is used to induce fluorescence, following two-photon excitation (TPE), from hydroxyl (OH) radicals that are present in premixed laminar flames. The experimental TPE and one-photon fluorescence spectra resulting from broadband excitation into the (0,0) band of the OH A(2)∑(+)-X(2)Π system are compared to simulated spectra. Additionally, the effects of non-transform-limited femtosecond pulses on TPE efficiency is investigated.     

基于瞬态光栅频率分辨光学开关法测量飞秒脉冲的研究

超宽光谱的飞秒脉冲测量一直是超快激光领域的重要研究方向之一.常规的飞秒脉冲自相关方法是通过测量自相关倍频信号来获得,而倍频信号具有波长选择性,不同中心波长的飞秒脉冲测量需要更换不同的倍频晶体,十分不方便.因此,提出了一种改进型的瞬态光栅频率分辨光学开关(TG-FROG)方法用于测量飞秒脉冲.该方法结合四波混频和频率分辨光学开关方法,其基本过程是将待测脉冲分为三束,其中两束脉冲经过精密的延时控制并聚焦在光学介质上达到时空重合,利用三阶非线性效应产生稳定的瞬态光栅作为开关光;另一束脉冲作为探测光与产生的瞬态光栅进行相互作用产生一个信号光,使用光谱仪对该信号光的光谱与延迟时间进行测量,并通过反演迭代算法处理而获取待测飞秒脉冲的光谱与电场信息.该方法只需要待测光的功率密度达到三阶非线性效应就可以实现测量,因此可以应用于任意中心波长的飞秒脉冲测量.利用该方法对中心波长分别为800 nm, 400 nm的飞秒脉冲,以及超连续亚10 fs的周期量级超宽光谱飞秒脉冲进行了测量,并与常规的干涉自相关仪器测量结果进行了比较,所得测量结果基本一致.实验结果表明,建立的基于TG-FROG方法对不同中心波长,不同脉冲宽度的飞秒脉冲测量是十分有效的.     

基于多光子脉冲内干涉相位扫描法对飞秒激光脉冲进行相位测量和补偿的研究

研制了一套基于多光子脉冲内干涉相位扫描方法的可以同时对飞秒激光脉冲进行相位测量和补偿的实验系统装置.实验中,通过自主研发的LabVIEW程序控制液晶空间光调制器和光纤光谱仪,对待测飞秒激光脉冲施加相位扫描,并同时记录受到调制的飞秒激光脉冲的倍频光谱,得到了多光子脉冲内干涉相位扫描(MIIPS)轨迹图.通过MIIPS轨迹图的三次测量和迭代运算,还原出了经过预先啁啾调制的中心波长约为810 nm、重复频率为1 kHz的飞秒激光脉冲的光谱相位,测量精度在0.1 rad以内.根据测量结果,利用液晶空间光调制器对该飞秒激光脉冲进行相位补偿,得到了近似傅里叶变换极限的飞秒激光脉冲.这一装置将在多光子显微成像、脉冲整形、飞秒激光光谱学等众多领域发挥重要作用.     

Attosecond pump probe: exploring ultrafast electron motion inside an atom

The attosecond pump probe, in close analogy to the standard femtosecond probing technique, has been proposed and theoretically demonstrated with its application to explore ultrafast electron motions inside atoms. We have performed realistic modeling for the full dynamics of both the femtosecond pumping and the attosecond probing processes. Our simulations have illustrated that an ultrashort oscillation period of 2.0 fs can be mapped out for a wave packet in low-lying excited states of the helium atom. This opens the prospect of a wealth of similar pump probe experiments to examine ultrafast electronic or atomic motions.     

Investigation of ultrafast dynamics of CdTe quantum dots by femtosecond fluorescence up-conversion spectroscopy

The ultrafast carrier relaxation processes in CdTe quantum dots are investigated by femtosecond fluorescence upconversion spectroscopy.Photo-excited hole relaxing to the edge of the forbidden gap takes a maximal time of ～ 1.6 ps with exciting at 400 nm,depending on the state of the photo-excited hole.The shallow trapped states and deep trap states in the forbidden gap are confirmed for CdTe quantum dots.In addition,Auger relaxation of trapped carriers is observed to occur with a time constant of ～ 5 ps.A schematic model of photodynamics is established based on the results of the spectroscopy studies.Our work demonstrates that femtosecond fluorescence up-conversion spectroscopy is a suitable and effective tool in studying the transportation and conversion dynamics of photon energy in a nanosystem.     

Femtosecond pump-probe photoionization-photofragmentation spectroscopy of azobenzene cation

We report the studies of ultrafast dynamics of azobenzene cations using femtosecond photoionization-photofragmentation spectroscopy. In our experiment,a femtosecond pump pulse first prepares an ensemble of azobenzene cations via photoionization of neutrals. A delayed probe pulse then brings the evolving ionic system to higher states that ultimately undergo ion fragmentation. The dynamics is followed by monitoring either the parent-ion depletion or fragment-ion formation as a function of the pump-probe delay time. The observed transients for azobenzene cations are characterized by a constant ion depletion modulated by a rapidly damped oscillatory signal with a period of about 1 ps. Theoretical calculations suggest that the oscillation arises from a vibration motion along the twisting inversion coordinate involving displacements in CNNC and phenyl-ring torsions. The oscillation is damped rapidly with a time constant of about 1.2 ps,suggesting that energy dissipation from the active mode to bath modes takes place on this time scale.     

超快微光分子光谱探测技术研究

按照超快极微弱分子吸收光谱学,荧光光谱学,时间分辨光谱学以及偏振荧光光谱学探测特性,设计、集成组建了能够探测紫外－可见－红外快到飞秒时间分辨的单分子光学事件的激光瞬态光谱仪.其光源有从300 nm到3000 nm连续可调的飞秒激光器、纳秒氢灯及连续氙灯.光谱分辨率达0.05 nm,在泵浦探测差异吸收下有小于150 fs的时间分辨率.谱仪能够实时给出光谱曲线及生物分子组分寿命.利用该谱仪探测了PSⅡCC,PSⅡRC的能量传递动力学.在83 K温度下PSⅡCC中的β-Car分子接收507 nm光能,以单步跃迁和随机转移的方式通过Chl a641.5637/638分子传递光能到反应中心Chl a683.2680/681,平均传能时间为77 ps,有59.94％的组分用355 ps时间电荷重组.在PSⅡRC中的β-Car分子接收507 nm光能,由Chl a641.5637/638分子传递光能通过Chl a678.2675.5到反应中心,平均传能时间为88.5 ps.在83 K温度下,反应中心复合物离子对;P680+·pheo-］平均再复合寿命为19.35 ns.     

Application of a femtosecond self-sustaining mode-locked Ti:sapphire laser to the field of laser scanning confocal microscopy

Developments in ultrafast Ti:sapphire laser technology can be applied in the investigation of nonlinear optical processes. We describe the application of a self-sustaining femtosecond Ti:sapphire laser as an illumination source in the field of confocal laser scanning fluorescence microscopy (LSM). We present spectra for various fluorescent stains under two-photon excitation and present LSM images of stained samples under mode-locked illumination. The potential for such a system as a non-destructive technique for studying live cells in biomedical research is discussed.     

Wavelength-tunable ultrashort-pulse output of a photonic-crystal fiber designed to resolve ultrafast molecular dynamics

Wavelength-tunable 100 fs pulses generated through the soliton self-frequency shift in a photonic-crystal fiber are employed to visualize femtosecond coherence and population relaxation dynamics in molecular aggregates by means of time-resolved sum-frequency generation. This technique reveals an ultrafast dephasing of coherent molecular excitations with a phase relaxation time of about 120 fs and resolves an ultrafast switching of the nonlinear-optical response of molecular aggregates.     

Ultrafast spectroscopy of excitons in single-walled carbon nanotubes

We studied the femtosecond dynamics of photoexcitations in films containing semiconducting and metallic single-walled carbon nanotubes (SWNTs), using various pump-probe wavelengths and intensities. We found that confined excitons and charge carriers with subpicosecond dynamics dominate the ultrafast response in semiconducting and metallic SWNTs, respectively. Surprisingly, we also found from the exciton excited state absorption bands and multiphoton absorption resonances in the semiconducting nanotubes that transitions between subbands are allowed; this unravels the important role of electron-electron interaction in SWNT optics.