间二氯苯的激发态动力学

利用飞秒分辨的激光泵浦-探测技术结合飞行时间质谱检测方法对间二氯苯分子的激发态动力学进行研究. 在270 nm泵浦, 810 nm探测条件下首次得到了第一单重激发态S₁(¹B₁)的寿命. 碎片离子C₆H₄Cl⁺主要来源于母体离子的解离, 属于电离解离(ID)机理. 实验得到的离子信号随泵浦-探测延时时间呈指数衰减并伴有周期性的振荡, 这种振荡属于量子拍频现象.     

用超短脉冲激光研究1,3-二氯苯激发态动力学

利用啁啾脉冲放大技术建立了一套掺钛蓝宝石飞秒激光放大系统,该系统输出中心波长808nm,单脉冲能量8mJ,脉冲宽度60fs,脉冲重复频率20Hz.利用飞秒激光泵浦-探测及分子束技术,结合飞行时间质谱,对1,3-二氯苯分子的激发态动力学过程进行了研究,实验中观察到该分子能级间的量子拍频现象,并获得了第一单重激发态寿命及其拍频频率,阐述了飞秒激光场下间位二氯苯分子的电离解离机理.     

丙硫咪唑的离子/中性碎片复合物中间体质谱碎裂

报道了丙硫咪唑（5-丙硫基-苯并咪唑-2-氨基甲酸甲酯）的电子轰击质谱。利用串联质谱的低能碰撞诱导解离（CID）技术研究了此化合物的单分子解离，并提出了可能的离子／中性碎片复合物中间体碎裂机理，用来解释在质谱碎裂过程中出现的氢迁移（尤其是远距离的氢迁移）现象。     

苯乙烯-马来酸酐本体自由基共聚合反应机理

应用络合-解离模型和络合参与模型，证明在70～140℃区间内苯乙烯-马来酸酐本体自由基共聚合反应属于络合-解离机理，理论结果与实验数据相吻合；而络合-参与模型与实验数据偏差较大．结果表明：随着温度的升高，络合物分子的聚合反应活性提高，链端自由基对组成络合物分子的单体选择性增强，生成交替共聚物的程度增大．     

丙烯酸分子的激发态超快预解离动力学

利用飞秒泵浦-探测技术结合飞行时间质谱(TOF-MS),研究了丙烯酸分子被200nm泵浦光激发到第二电子激发态(S2)后的超快预解离动力学.采集了母体离子和碎片离子的时间分辨质谱信号,并利用动力学方程对时间分辨离子质谱信号进行拟合和分析,揭示了预解离通道的存在.布居在S2激发态的分子通过快速的内转换弛豫到第一电子激发态(S1),时间常数为210fs,随后再经内转换从S1态弛豫到基态(S0)的高振动态,时间常数为1.49ps.分子最终在基态高振动态势能面上发生C-C键和C-O键的断裂,分别解离生成H2C=CH和HOCO、H2C=CHCO和OH中性碎片,对应的预解离时间常数分别约为4和3ps.碎片离子的产生有两个途径,分别来自于母体离子的解离和基态高振动态势能面上中性碎片的电离.     

离子速度成像方法研究C8H17Br分子的光解动力学

用离子速度成像方法, 研究了长链C8H17Br分子在234 nm激光下的光解过程. 通过2+1共振增强多光子电离探测了两种光解产物Br*(2P1/2)和Br(2P3/2), 得到了它们的相对量子产率. 从光解产物Br*(2P1/2)和Br(2P3/2)的速度图像得到了能量和角度分布. 并根据相对量子产率和角度分布, 计算了不同解离通道的比例. 实验发现C8H17Br分子解离过程中大部分能量都转化为内能, 该能量分配可以较好地用软反冲模型来解释, 并分析了这种能量分配跟烷基大小的关系.     

丙硫咪唑的离子／中性碎片复合物中间体质谱破裂

报道了丙硫咪唑（５－丙硫基－苯并咪唑－２氨基甲酸酯）的电子轰击质谱。利用串联质谱的低能碰撞诱导解离（ＣＩＤ）技术研究了此化合物的单分子解离，并提出了可能的离子／中性碎片复合筘间体碎裂机理，用来解释在质谱碎裂过程中出现的氢迁移（尤其是远距离的氢迁移）现象。     

含时波包法研究RbI光电子能谱的脉冲延迟效应

利用含时波包方法模拟不同泵浦-探测延迟时间下RbI分子1+3多光子电离时间分辨光电子能谱(TRPES). 模拟过程同时考虑了三光子电离过程和自电离过程. 计算结果表明, 泵浦-探测延迟时间的改变会影响光电子能谱(PES)的形状, 而这种影响实质上是由于强场的存在改变了相关势能面的位置以及势能面之间的交叉所导致的.     

飞秒受激拉曼光谱技术

飞秒受激拉曼光谱（femtosecond stimulated raman spectroscopy,FSRS）是一种新型的非线性振动光谱技术.它使用两束重叠的窄带拉曼泵浦和宽带探测脉冲激光束,利用外差式检波方法在探测光方向上进行信号探测.FSRS既可以用来探测分子电子基态的振动动力学,也可以用来探测分子电子激发态的振动动力学,比如同质异构类反应.即使荧光背景很强的分子,也可以用FSRS来研究.FSRS可以用三阶微扰的波包图像来描绘.单从相位匹配条件出发,共有48项对应于FSRS过程,但是其中只有8项满足共振条件.可以用3种方法来描述这8项：双时间线拉曼图、封闭时间路径环路图和四波混频的能级图.进一步分析表明,这8项可以分成4类,即SRS（I）,SRS（II）,IRS（I）和IRS（II）,其中SRS代表受激拉曼散射,IRS代表反转拉曼散射.SRS（I）可以用来解释自发拉曼散射,但是其余的SRS（II）、IRS（I）和IRS（II）三项只在受激拉曼光谱中存在.FSRS光谱中SRS（I）过程产生的是斯托克斯拉曼谱线,而IRS（I）过程则产生的是反斯托克斯谱线.其余的两项SRS（II）和IRS（II）只是产生很宽的背景基线,基本和我们感兴趣的观测量不相关.使用简谐振动模型,我们可以得到三阶微扰极化率的四时间相关函数的解析表达式.我们讨论了FSRS光谱之所以能够得到高时间分辨率和高频率分辨率的物理原理.在文章中,我们还就以下研究做了计算与实验结果的比较：（a）荧光性罗丹明6G的共振FSRS谱和（b）CDCl3分子非共振脉冲泵浦光制备的相干振动态的二维FSRS谱.计算得到的结果与实验十分吻合,同时在理论上证明了CDCl3二维FSRS光谱中级联效应是占主导作用的.     

离子速度影像法研究n-C7H15Br分子光解反应动力学

利用离子速度成像方法, 研究n-C7H15Br分子在231～239 nm范围内几个波长处的光解离动力学. 通过同一束激光经(2+1)共振多光子电离(REMPI)过程探测光解碎片Br(2P3/2)和Br*(2P1/2), 得到了不同激光波长处的离子速度分布图像, 从而获得C7H15Br光解产物的能量分配和角度分布. 结合各向异性参数和量子产率, 计算了n-C7H15Br分子在234 nm波长下不同解离通道的比例. 实验表明光解产物的能量分配可以用冲击模型中的软碰撞模型来解释. 实验还发现, 各向异性参数β(Br*)的值对光波长变化很敏感, 这是由电子激发态的绝热和非绝热过程决定的.     

Laser-assisted collisional effects in non-linear optical phenomena: Six-wave difference frequency mixing in mercury vapor

Laser-assisted collisional phenomena have been observed in non-linear optical studies of harmonic generation in Hg vapor. Spectral profiles showing the characteristic assymetric broadening, which are the signature of such effects, have been obtained for both single- laser and two-laser pump-probe experiments. The latter clearly shows that harmonic radiation is only produced by the application of a “dressing” laser field.     

IR double resonance experiments with size selected clusters for identification of isomers

Infrared photodissociation spectra of (CH₃OH) _n clusters (n=2, 3 and 6) and the mixed dimer C₂H₄ · CH₃COCH₃ are presented. The clusters are generated in a supersonic jet expansion and size selected by scattering from a helium atomic beam combined with mass spectrometric detection. Continuous CO₂-lasers are used to vibrationally excite the molecules in the cluster leading to rapid dissociation of the complex. Various dissociation peaks that are found in single-laser dissociation spectra can be assigned unambigously in a pump-probe experiment with two lasers to either different isomers (acetone-ethene dimer) or splitted lines of one isomer (methanol hexamer). For size distributions, the method is able to select contributions of single masses which is demonstrated for mixtures of methanol dimers and trimers.     

飞秒泵浦-探测实验中量子拍频现象的数据处理

The pump-probe experiments for 1,3-dichlorobenzene in gas phase have been performed by femtosecond multiphoton ionization mass spectra at a pump pulse of 270 nm and a probe pulse of 810 nm by using our homebuilt femtosecond laser system. The models for the exponential process and quantum beat are presented to extract the photodissociation dynamics information from the data. A fitting and analyzing software which is programmed by graphical language LabVIEW has been developed for the experimental data. The Convolution, Levenberg Marquardt,and Deconvolution mathematics VIs of LabVIEW are used in this program to make the program much simpler than using other programming languages. The experimental data have been well fitted with this program. The results provide the lifetime of excited-state S1 and the frequency of quantum beat.     

Influence of Higher Excited Singlet States on Ultrafast Exciton Motion in Pigment-Protein Complexes

Abstract— Numerical simulations of the ultrafast exciton motion in photosynthetic antenna complexes are used to reproduce measured data of optical pump-probe experiments. Emphasis is put on a chlorophyll aL/chlorophyll b dimer of the light-harvesting complex of the photosystem II of higher plants (LHC-II). To account for intramolecular excited-state absorption the standard exciton theory is extended to the inclusion of a second higher excited singlet state per chlorophyll molecule. The density matrix theory is applied to describe the dissipative dynamics of excitons. Different mechanisms for energy relaxation and dephasing including pure dephasing processes are discussed. As a result, a further refinement of earlier calculations on the one-color pump-probe spectra at the LHC-II can be presented. In particular, the presence of non-Markovian effects with respect to the exciton-vibrational interaction in the LHC-II, discovered previously in the two-color pump-probe spectrum, is demonstrated here for the one-color pump-probe case.     

Time-resolved photoion and photoelectron imaging of NO(2)

Time-resolved photoion and photoelectron velocity mapped images from NO(2) excited close to its first dissociation limit [to NO(X(2)Pi) + O((3)P(2))] have been recorded in a two colour pump-probe experiment, using the frequency-doubled and frequency-tripled output of a regeneratively amplified titanium-sapphire laser. At least three processes are responsible for the observed transient signals; a negative pump-probe signal (corresponding to a 266 nm pump), a very short-lived transient close to the cross-correlation of the pump and probe pulses but on the 400 nm pump side, and a longer-lived positive pump-probe signal that exhibits a signature of wavepacket motion (oscillations). These transients have two main origins; multiphoton excitation of the Rydberg states of NO(2) by both 266 and 400 nm light, and electronic relaxation in the 1(2)B(2) state of NO(2), which leads to a quasi-dissociated NO(2) high in the 1(2)A(1) electronic ground state and just below the dissociation threshold. The wavepacket motion that we observe is ascribed to states exhibiting free rotation of the O atom about the NO moiety. These states, which are common for loosely bound systems such as a van der Waals complex but unusual for a chemically-bound molecule, have previously been observed in the frequency domain by optical double resonance spectroscopy but never before in the time domain.     

Interpreting closed-loop learning control of molecular fragmentation in terms of wave-packet dynamics and enhanced molecular ionization

We interpret a molecular fragmentation experiment using shaped, ultrafast laser pulses in terms of enhanced molecular ionization during dissociation. A closed-loop learning control experiment was performed to maximize the CF3+CH3+ production ratio in the dissociative ionization of CH3COCF3. Using ab inito molecular structure calculations and quasistatic molecular ionization calculations along with data from pump-probe experiments, we identify the primary control mechanism which is quite general and should be applicable to a broad class of molecules.     

A first principles approach to optimal control

This article shows that by using ab initio or first principle calculations it is possible to obtain reliable ingredients needed to simulate pump-probe and optimal control experiments. Our experimental challenge is to elucidate the reaction mechanism behind an optimal pulse tailored to maximize ionization in the system CpMn(CO)₃, while avoiding CO dissociation. Starting from MRCI/CASSCF potential energy curves calculated along the relevant CO fragmentation channel, we use the resulting MRCI wave function to estimate non-adiabatic couplings, as well as neutral-to-neutral and neutral-to-ionic dipole couplings. The state-of-the-art potentials and couplings serve to perform wave packet propagations which simulate the femtosecond pump-probe spectra that explain the features shown in the experimental optimal pulse.     

The influence of cluster formation on the photodissociation of sulfur dioxide: excitation to the E state

A femtosecond pump-probe technique was employed to study the dissociation dynamics of sulfur dioxide and sulfur dioxide clusters in real time. Dissociation is initiated by a multiphoton scheme that populates the E state. The SO(2) (+) transient is fit to a biexponential decay comprising a fast and a slow component of 230 fs and 8 ps, respectively. The SO(+) transient consists of a growth component of 225 fs as well as a subsequent decay of 373 fs. The pump-probe response obtained from the monomer clearly shows the predissociative cleavage of a S-O bond. Upon cluster formation, a sequential increase in the fast decay component is observed for increasing cluster size, extending to 435 fs for (SO(2))(4) (+). The transient response of cluster dissociation products SO(SO(2))(n) (+), where n=1-3, reflects no growth component indicating that formation proceeds through the ion state. Therefore, cluster formation results in a caging effect, which impedes the dissociation process. Further direct evidence for our proposed mechanism is obtained by a technique that employs a comparison of the amplitude coefficients of each respective component of the fit. This method makes possible the determination of branching ratios of competing relaxation processes and thereby the influence of cluster formation on each can be resolved. The caging effect is attributed to a steric hindrance placed on the SO(2) chromophore, preventing it from attaining a linear geometry necessary for dissociation.     

Coherent Vibrational and Dissociation Dynamics of Polyatomic Radical Cations

The ultrafast dynamics of polyatomic radical cations contribute to important processes including energy transfer in photovoltaics, electron transfer in photocatalysis, radiation-induced DNA damage, and chemical reactions in the upper atmosphere and space. Probing these dynamics in the gas phase is challenging due to the rapid dissociation of polyatomic radical cations following electron removal, which arises from excess electronic excitation of the molecule during the ionization process. This Concept article introduces the reader to how the pump-probe technique of femtosecond time-resolved mass spectrometry (FTRMS) can overcome this challenge to capture coherent vibrational dynamics on the femtosecond timescale in polyatomic radical cations and enable the analysis of their dissociation pathways. Examples of FTRMS applied to three families of polyatomic radical cations are discussed.     

Self-trapping of the N-H vibrational mode in alpha-helical polypeptides

Recent calculations on the formation of self-trapped amide group vibrational states in alpha-helical polypeptides [J. Chem. Phys. 124, 134907 (2006)] are extended to the amide N-H normal mode vibrations. First, the adiabatic N-H vibrational single- and two-exciton states are examined by treating the longitudinal chain coordinates as parameters. Then, in using the multiconfiguration time-dependent Hartree method coupled exciton-chain vibrational quantum dynamics are accounted for. Based on the respective exciton-chain vibrational wave function propagation the infrared transient absorption related to a sequential pump-probe experiment is calculated. The modulation of local amide vibrational energies by the longitudinal chain coordinates is found to have a pronounced effect on the broadening of absorption lines. Moreover, the ultrafast exciton transfer in the system is studied in order to characterize the dynamics of the self-trapped single-exciton states on a time scale below 10 ps.