Two-dimensional spectroscopy of electronic couplings in photosynthesis

Time-resolved optical spectroscopy is widely used to study vibrational and electronic dynamics by monitoring transient changes in excited state populations on a femtosecond timescale. Yet the fundamental cause of electronic and vibrational dynamics--the coupling between the different energy levels involved--is usually inferred only indirectly. Two-dimensional femtosecond infrared spectroscopy based on the heterodyne detection of three-pulse photon echoes has recently allowed the direct mapping of vibrational couplings, yielding transient structural information. Here we extend the approach to the visible range and directly measure electronic couplings in a molecular complex, the Fenna-Matthews-Olson photosynthetic light-harvesting protein. As in all photosynthetic systems, the conversion of light into chemical energy is driven by electronic couplings that ensure the efficient transport of energy from light-capturing antenna pigments to the reaction centre. We monitor this process as a function of time and frequency and show that excitation energy does not simply cascade stepwise down the energy ladder. We find instead distinct energy transport pathways that depend sensitively on the detailed spatial properties of the delocalized excited-state wavefunctions of the whole pigment-protein complex.     

Tomographic imaging of molecular orbitals

Single-electron wavefunctions, or orbitals, are the mathematical constructs used to describe the multi-electron wavefunction of molecules. Because the highest-lying orbitals are responsible for chemical properties, they are of particular interest. To observe these orbitals change as bonds are formed and broken is to observe the essence of chemistry. Yet single orbitals are difficult to observe experimentally, and until now, this has been impossible on the timescale of chemical reactions. Here we demonstrate that the full three-dimensional structure of a single orbital can be imaged by a seemingly unlikely technique, using high harmonics generated from intense femtosecond laser pulses focused on aligned molecules. Applying this approach to a series of molecular alignments, we accomplish a tomographic reconstruction of the highest occupied molecular orbital of N2. The method also allows us to follow the attosecond dynamics of an electron wave packet.     

Correlated electron emission in multiphoton double ionization

Electronic correlations govern the dynamics of many phenomena in nature, such as chemical reactions and solid state effects, including superconductivity. Such correlation effects can be most clearly investigated in processes involving single atoms. In particular, the emission of two electrons from an atom--induced by the impact of a single photon, a charged particle or by a short laser pulse--has become the standard process for studies of dynamical electron correlations. Atoms and molecules exposed to laser fields that are comparable in intensity to the nuclear fields have extremely high probabilities for double ionization; this has been attributed to electron-electron interaction. Here we report a strong correlation between the magnitude and the direction of the momentum of two electrons that are emitted from an argon atom, driven by a femtosecond laser pulse (at 38 TW cm(-2)). Increasing the laser intensity causes the momentum correlation between the electrons to be lost, implying that a transition in the laser-atom coupling mechanism takes place.     

偶氮苯分子光致异构化的研究

偶氮苯类化合物分子在一定波长的光照射下会产生顺式反式的结构变化,利用东南大学分子逊实验室提出的薄膜实时演变分析技术和基于此技术所研制的系统对这一现象进行研究。我们发现甩膜法制备的异丁烯酸（２－对硝基偶氮苯）乙酯Ｐ１２薄膜在光照下的折射率的变化是由于偶氮苯分子的光致异构化造成的,用３６０ｎｍ光照使偶氮苯分子产生由反式到顺式的结构变化,再用４５０ｎｍ光照使偶氮苯分子产生由顺式到反式的结构变化。在薄膜实     

基于LabVIEW的飞秒超快动力学数据采集系统

飞秒泵浦-探测技术是一种可以在原子运动时间尺度上实时观测化学反应的有力手段.在飞秒泵浦-探测技术基础上发展起来的分子超快动力学是当前分子反应动力学研究领域的热点和焦点之一.在分子超快动力学的研究过程中,往往需要建立一套高速的数据采集、处理以及分析系统.用LabVIEW程序编写该系统的软件部分,能够完成对飞行时间质谱及其谱峰面积的实时采集.本文介绍了该系统的硬件组成以及软件设计,并把该系统用于邻二氯苯的超快动力学研究中,观察到了二氯苯母体和碎片的寿命.     

Chiral recognition in dimerization of adsorbed cysteine observed by scanning tunnelling microscopy

Stereochemistry plays a central role in controlling molecular recognition and interaction: the chemical and biological properties of molecules depend not only on the nature of their constituent atoms but also on how these atoms are positioned in space. Chiral specificity is consequently fundamental in chemical biology and pharmacology and has accordingly been widely studied. Advances in scanning probe microscopies now make it possible to probe chiral phenomena at surfaces at the molecular level. These methods have been used to determine the chirality of adsorbed molecules, and to provide direct evidence for chiral discrimination in molecular interactions and the spontaneous resolution of adsorbates into extended enantiomerically pure overlayers. Here we report scanning tunnelling microscopy studies of cysteine adsorbed to a (110) gold surface, which show that molecular pairs formed from a racemic mixture of this naturally occurring amino acid are exclusively homochiral, and that their binding to the gold surface is associated with local surface restructuring. Density-functional theory calculations indicate that the chiral specificity of the dimer formation process is driven by the optimization of three bonds on each cysteine molecule. These findings thus provide a clear molecular-level illustration of the well known three-point contact model for chiral recognition in a simple bimolecular system.     

Direct frequency comb spectroscopy in the extreme ultraviolet

The development of the optical frequency comb (a spectrum consisting of a series of evenly spaced lines) has revolutionized metrology and precision spectroscopy owing to its ability to provide a precise and direct link between microwave and optical frequencies. A further advance in frequency comb technology is the generation of frequency combs in the extreme-ultraviolet spectral range by means of high-harmonic generation in a femtosecond enhancement cavity. Until now, combs produced by this method have lacked sufficient power for applications, a drawback that has also hampered efforts to observe phase coherence of the high-repetition-rate pulse train produced by high-harmonic generation, which is an extremely nonlinear process. Here we report the generation of extreme-ultraviolet frequency combs, reaching wavelengths of 40?nanometres, by coupling a high-power near-infrared frequency comb to a robust femtosecond enhancement cavity. These combs are powerful enough for us to observe single-photon spectroscopy signals for both an argon transition at 82?nanometres and a neon transition at 63?nanometres, thus confirming the combs' coherence in the extreme ultraviolet. The absolute frequency of the argon transition has been determined by direct frequency comb spectroscopy. The resolved ten-megahertz linewidth of the transition, which is limited by the temperature of the argon atoms, is unprecedented in this spectral region and places a stringent upper limit on the linewidth of individual comb teeth. Owing to the lack of continuous-wave lasers, extreme-ultraviolet frequency combs are at present the only promising route to extending ultrahigh-precision spectroscopy to the spectral region below 100?nanometres. At such wavelengths there is a wide range of applications, including the spectroscopy of electronic transitions in molecules, experimental tests of bound-state and many-body quantum electrodynamics in singly ionized helium and neutral helium, the development of next-generation 'nuclear' clocks and searches for variation of fundamental constants using the enhanced sensitivity of highly charged ions.     

Monitor and control of neuronal activities with femtosecond pulse laser

Combined with the fluorescence labeling technique, two-photon microscopy excited with femtosecond pulse laser has become an important tool for neuroscience research. In this research, the calcium signals from neurons in rat cortex slice were monitored by a custom-built two-photon microscopy, and the spontaneous calcium signals and the pharmacological responses as well as the responses to femtosecond pulse laser stimulation were recorded. The results showed that the amplitude of the cal- cium signals increased in direct proportion to the corresponding electrical activities. Glutamate induced a calcium transient, but continuous application resulted in smaller response. Simultaneous monitoring of neuronal populations distinguished the neurons of different microcircuits. The femtosecond pulse laser induced local or global calcium signals in the pyramidal neurons. The approach of interrogation and control of neural activities using femtosecond pulse laser is non-contact, nondestructive, repeatable, and without any additional substrates, which will contribute to the development of neuroscience.     

飞秒激光在蓝宝石晶体表面加工微细结构的实验研究

由于蓝宝石晶体具有很高的硬度和耐磨蚀性,很难进行机械和化学腐蚀加工。笔者利用波长780 nm、频率1 kHz和脉冲宽度164 fs的飞秒脉冲激光在蓝宝石晶体表面进行了微细结构加工的实验研究。采用飞秒激光静态照射蓝宝石晶体表面,通过飞秒激光烧蚀孔的直径和脉冲能量的关系,计算了飞秒激光烧蚀蓝宝石晶体的两种烧蚀状态下的烧蚀阈值和有效烧蚀半径。通过直线扫描实验,在不同实验条件下在蓝宝石晶体表面加工微槽,获得微槽的宽度和深度与飞秒激光主要参数之间的关系。研究结果表明,微槽的加工表面可通过增加扫描次数而得到明显的提高,且扫描次数的增加对微槽的宽度和深度基本无影响。利用聚焦的飞秒激光束沿着轨迹扫描,在蓝宝石晶体表面加工出比较清洁的微小结构,可以为实现微结构的精密加工提供指导。     

Molecular spectroscopy: complexity of excited-state dynamics in DNA

Absorption of ultraviolet light by DNA is known to lead to carcinogenic mutations, but the processes between photon absorption and the photochemical reactions are poorly understood. In their study of the excited-stated dynamics of model DNA helices using femtosecond transient absorption spectroscopy, Crespo-Hernández et al. observe that the picosecond component of the transient signals recorded for the adenine-thymine oligonucleotide (dA)18.(dT)18 is close to that for (dA)18, but quite different from that for (dAdT)9.(dAdT)9; from this observation, they conclude that excimer formation limits excitation energy to one strand at a time. Here we use time-resolved fluorescence spectroscopy to probe the excited-state dynamics, which reveals the complexity of these systems and indicates that the interpretation of Crespo-Hernández et al. is an oversimplification. We also comment on the pertinence of separating base stacking and base pairing in excited-state dynamics of double helices and question the authors' assignment of the long-lived signal component found for (dA)18.(dT)18 to adenine excimers.     

有关气体分子在沸石上吸附的理论模型

本文用两参数的理论模型关联了气体分子在沸石上的吸附过程，两个参数的值可通过真空重量法获得的饱和吸附量求得。与传统的从瞬时吸附曲线求得的扩散系数相比，本模型中的参数不会因操作而变化，因此能有效地表征吸附过程。     

Observation and interpretation of a time-delayed mechanism in the hydrogen exchange reaction

Extensive theoretical and experimental studies have shown the hydrogen exchange reaction H+H2 --> H2+H to occur predominantly through a 'direct recoil' mechanism: the H--H bonds break and form concertedly while the system passes straight over a collinear transition state, with recoil from the collision causing the H2 product molecules to scatter backward. Theoretical predictions agree well with experimental observations of this scattering process. Indirect exchange mechanisms involving H3 intermediates have been suggested to occur as well, but these are difficult to test because bimolecular reactions cannot be studied by the femtosecond spectroscopies used to monitor unimolecular reactions. Moreover, full quantum simulations of the time evolution of bimolecular reactions have not been performed. For the isotopic variant of the hydrogen exchange reaction, H+D2 --> HD+D, forward scattering features observed in the product angular distribution have been attributed to possible scattering resonances associated with a quasibound collision complex. Here we extend these measurements to a wide range of collision energies and interpret the results using a full time-dependent quantum simulation of the reaction, thus showing that two different reaction mechanisms modulate the measured product angular distribution features. One of the mechanisms is direct and leads to backward scattering, the other is indirect and leads to forward scattering after a delay of about 25 femtoseconds.     

Photoselective adaptive femtosecond quantum control in the liquid phase.

Coherent light sources can be used to manipulate the outcome of light-matter interactions by exploiting interference phenomena in the time and frequency domain. A powerful tool in this emerging field of 'quantum control' is the adaptive shaping of femtosecond laser pulses, resulting, for instance, in selective molecular excitation. The basis of this method is that the quantum system under investigation itself guides an automated search, via iteration loops, for coherent light fields best suited for achieving a control task designed by the experimenter. The method is therefore ideal for the control of complex experiments. To date, all demonstrations of this technique on molecular systems have focused on controlling the outcome of photo-induced reactions in identical molecules, and little attention has been paid to selectively controlling mixtures of different molecules. Here we report simultaneous but selective multi-photon excitation of two distinct electronically and structurally complex dye molecules in solution. Despite the failure of single parameter variations (wavelength, intensity, or linear chirp control), adaptive femtosecond pulse shaping can reveal complex laser fields to achieve chemically selective molecular excitation. Furthermore, our results prove that phase coherences of the solute molecule persist for more than 100 fs in the solvent environment.     

N2和O2分子的强场光电离

本研究工作主要采用超声分子束、飞秒激光与飞行时间(TOF)质谱等实验技术相结合的方法研究了N_2和O_2分子在飞秒强激光场作用下的光电离.通过分析N_2和O_2分子的飞行时间质谱及碎片离子产额,得到了离子产额的激光强度依赖关系、激光极化效应和偏振度效应,并结合强场理论知识对光电离机制进行了细致地分析.     

Biasing reaction pathways with mechanical force

During the course of chemical reactions, reactant molecules need to surmount an energy barrier to allow their transformation into products. The energy needed for this process is usually provided by heat, light, pressure or electrical potential, which act either by changing the distribution of the reactants on their ground-state potential energy surface or by moving them onto an excited-state potential energy surface and thereby facilitate movement over the energy barrier. A fundamentally different way of initiating or accelerating a reaction is the use of force to deform reacting molecules along a specific direction of the reaction coordinate. Mechanical force has indeed been shown to activate covalent bonds in polymers, but the usual result is chain scission. Here we show that mechanically sensitive chemical groups make it possible to harness the mechanical forces generated when exposing polymer solutions to ultrasound, and that this allows us to accelerate rearrangement reactions and bias reaction pathways to yield products not obtainable from purely thermal or light-induced reactions. We find that when placed within long polymer strands, the trans and cis isomers of a 1,2-disubstituted benzocyclobutene undergo an ultrasound-induced electrocyclic ring opening in a formally conrotatory and formally disrotatory process, respectively, that yield identical products. This contrasts with reaction initiation by light or heat alone, in which case the isomers follow mutually exclusive pathways to different products. Mechanical forces associated with ultrasound can thus clearly alter the shape of potential energy surfaces so that otherwise forbidden or slow processes proceed under mild conditions, with the directionally specific nature of mechanical forces providing a reaction control that is fundamentally different from that achieved by adjusting chemical or physical parameters. Because rearrangement in our system occurs before chain scission, the effect we describe might allow the development of materials that are activated by mechanical stress fields.     

基于纳飞秒双脉冲激光的蓝宝石蚀除研究

蓝宝石作为一种典型的宽带隙半导体材料具有良好的理化特性,在机械电子、航空航天、微电子等领域具有广阔的应用前景.本文提出采用纳飞秒双束激光进行蓝宝石加工的方法,利用飞秒脉冲峰值功率高的特性,通过多光子电离与碰撞电离,激发蓝宝石表面自由电子从而提高了蓝宝石对纳秒激光的吸收率,同时利用纳秒激光能量相对较大,技术成熟的优势,实现对蓝宝石材料的高质高效加工.为了揭示纳飞秒双束激光与蓝宝石材料的能量耦合机制,采用Fokker-Plank方程、Drude模型、双温模型对飞秒激光诱发的自由电子的演化过程及自由电子与入射激光之间的相互作用进行研究,并通过有限元仿真模拟了纳飞秒双激光与蓝宝石材料相互作用的能量耦合过程与蚀除过程,分析了纳飞秒双脉冲激光作用下,不同脉冲延时下等离子浓度的时空演化规律及其对入射激光吸收系数及反射率等表面光学特性的影响规律,揭示了纳飞秒双激光高效高质加工蓝宝石材料的机理.该研究对实现蓝宝石等宽带隙半导体等脆硬材料的高质高效加工具有重要意义.     

Adaptive subwavelength control of nano-optical fields

Adaptive shaping of the phase and amplitude of femtosecond laser pulses has been developed into an efficient tool for the directed manipulation of interference phenomena, thus providing coherent control over various quantum-mechanical systems. Temporal resolution in the femtosecond or even attosecond range has been demonstrated, but spatial resolution is limited by diffraction to approximately half the wavelength of the light field (that is, several hundred nanometres). Theory has indicated that the spatial limitation to coherent control can be overcome with the illumination of nanostructures: the spatial near-field distribution was shown to depend on the linear chirp of an irradiating laser pulse. An extension of this idea to adaptive control, combining multiparameter pulse shaping with a learning algorithm, demonstrated the generation of user-specified optical near-field distributions in an optimal and flexible fashion. Shaping of the polarization of the laser pulse provides a particularly efficient and versatile nano-optical manipulation method. Here we demonstrate the feasibility of this concept experimentally, by tailoring the optical near field in the vicinity of silver nanostructures through adaptive polarization shaping of femtosecond laser pulses and then probing the lateral field distribution by two-photon photoemission electron microscopy. In this combination of adaptive control and nano-optics, we achieve subwavelength dynamic localization of electromagnetic intensity on the nanometre scale and thus overcome the spatial restrictions of conventional optics. This experimental realization of theoretical suggestions opens a number of perspectives in coherent control, nano-optics, nonlinear spectroscopy, and other research fields in which optical investigations are carried out with spatial or temporal resolution.     

液压冲击压力峰值计算方法的探讨

目前国内均用能量法来计算液压冲击压力峰值,本文提出模拟计算法,即把油路系统模拟为单质量弹簧系统,建立数学模型,推导出压力峰值。用能量法所求之值为过渡过程中平均压力值,用模拟法所求之值为过渡过程中的瞬态最大值,因此,在计算压力峰值时,后者更接近问题的本质.     

飞秒激光烧蚀炸药的冲击压力数值模拟

飞秒激光能够在极短时间内烧蚀炸药产生高温高压等离子体,飞秒激光烧蚀炸药技术可用于精密加工炸药元件和安全处理废旧弹药.为深入探讨飞秒激光烧蚀炸药作用规律,采用非线性有限元计算方法,建立了飞秒激光烧蚀炸药过程的起爆计算模型,对飞秒激光烧蚀LX-17和LX-10两种炸药过程进行了数值模拟计算,获得了不同飞秒激光能量作用下等离子体和炸药中的压力分布规律.计算结果表明,在飞秒激光烧蚀炸药的过程中,烧蚀产物等离子体和激光作用区外附近炸药的初始压力较高,但是由于激光烧蚀区域极小,炸药内冲击波压力迅速衰减,没有发生起爆现象.