Ultrafast Coulomb explosion imaging of molecules and molecular clusters

Taking an image of their structure and a movie of their dynamics of small quantum systems have always been a dream of physicists and chemists. Laser-induced Coulomb explosion imaging (CEI) provides a great opportunity to make this dream a reality for small molecules or their aggregation —— clusters. The method is unique for identifying the atomic locations with ångstrom spatial resolution and capturing the structural evolution with a femtosecond time scale, in particular for imaging transient state products. This review summarizes the determination of three-dimensional equilibrium geometry of molecules and molecular cluster system through the reconstruction from the fragments momenta, and also shows that the dissociation dynamics on the complex potential energy surface can be tracked in real-time with the ultrafast CEI (UCEI). Furthermore, the detailed measurement and analysis procedures of the CEI, theoretical methods, exemplary results, and future perspectives of the technique are described.     

冷核聚变十五年

参考在美国麻省理工学院召开的第十届国际冷核聚变会议(ICCF 10)内容,对冷核聚变研究的现状作一简单介绍.国际原子能委员会(IAEA)分管聚变的官员(1995—2001年)T.J.Dolan在清华召开的ICCF 9国际会议上的总结会上提出五种重要的解释冷聚变现象的理论模型,其中有江兴流提出的涡旋动力学模型.涡旋动力学模型的主要论点在于:局域瞬态非平衡体系产生涡旋,而涡旋的内聚作用和极化效应,使体系内的粒子相互靠近,产生局域极化核反应和高度定向的轴向加速高能粒子.这种局域瞬态非平衡体系出现在电极微突起处或多层膜的非平衡点处.这一理论成功地解释了许多异常放热和核嬗变现象,因而受到了广泛重视.对涡旋动力学作以简单介绍. Many papers published in the 10th International Conference of Cold Fusion( MIT, Massachusetts .Aug. 2003) reveal the experimental results of excess heat with a few of products of nuclear reactions. Over the years it is become clear that there are new effects to be surfaced. Thomas J. Dolan listed several interesting theoretical ideas including the model of vortex dynamics proposed by Xingliu Jiang. This model says that excess heat and nuclear reactions in electrical discharge system and other transient...     

Low energy electron-driven damage in biomolecules

The damage induced by the impact of low energy electrons (LEE) on biomolecules is reviewed from a radiobiological perspective with emphasis on transient anion formation. The major type of experiments, which measure the yields of fragments produced as a function of incident electron energy (0.1-30 eV), are briefly described. Theoretical advances are also summarized. Several examples are presented from the results of recent experiments performed in the gas-phase and on biomolecular films bombarded with LEE under ultra-high vacuum conditions. These include the results obtained from DNA films and those obtained from the fragmentation of elementary components of the DNA molecule (i.e., the bases, sugar and phosphate group analogs and oligonucleotides) and of proteins (e.g. amino acids). By comparing the results from different experiments and theory, it is possible to determine fundamental mechanisms that are involved in the dissociation of the biomolecules and the production of single- and double-strand breaks in DNA. Below 15 eV, electron resonances (i.e., the formation of transient anions) play a dominant role in the fragmentation of all biomolecules investigated. These transient anions fragment molecules by decaying into dissociative electronically excited states or by dissociating into a stable anion and a neutral radical. These fragments can initiate further reactions within large biomolecules or with nearby molecules and thus cause more complex chemical damage. Dissociation of a transient anion within DNA may occur by direct electron attachment at the location of dissociation or by electron transfer from another subunit. Damage to DNA is dependent on the molecular environment, topology, type of counter ion, sequence context and chemical modifications.     

侧链基团对聚合物薄膜瞬态发光性能的影响

采用飞秒激光光谱技术比较研究了两种卟啉侧链聚合物:卟啉丙烯酸酯-苯乙烯共聚物P[(por)A-S]和卟啉铁(Ⅲ)丙烯酸酯-苯乙烯共聚物P[(por)FeA-S]的瞬态发光性能。并采用纳秒激光光谱技术测量了小分子卟啉(TPP)的荧光动力学过程。结果表明:P[(por)FeA-S]具有比P[(por)A-S]快得多的荧光弛豫过程,而P[(por)A-S]的荧光寿命远小于小分子卟啉的荧光寿命。对上述过程进行了分析,P[(por)A-S]的荧光衰变主要来源于聚合物分子链间的相互作用;而P[(por)FeA-S]的荧光衰变除了来源于聚合物分子链间的相互作用外,中央金属离子与配位体之间的电荷转移也对卟啉发色基团的激发态超快无辐射弛豫具有重要的影响,对上述过程的产生机理进行了讨论。     

Solvent effects on the intrinsic enhancement factors of the triplet exciplex generated by photoinduced electron transfer reaction between eosin Y and duroquinone

The spin dynamics of the duroquinone anion radical (DQ^?-) generated by photoinduced electron transfer reactions from triplet eosin Y (³EY^2-) to DQ have been studied by using transient absorption and pulsed EPR spectroscopy. Unusual net-absorptive electron spin polarization plus net-emissive polarization were observed, suggesting the production of the triplet exciplex or contact radical pair as the reaction intermediate. The kinetic parameters and intrinsic enhancement factors of the electron spin polarization were determined in various alcoholic solvents. The net-absorptive electron spin polarization was also observed in ethanol-water mixed solvents. The solvent effects on the radical yield are analysed on the basis of a stochastic Liouville equation established for the magnetic field effects on the radical yield. The zero-field splitting constants of the triplet exciplex are estimated from the solvent viscosity dependence of the enhancement factors due to spin-orbit coupling induced depopulation of the reaction intermediate.     

The photodetachment spectrum of OHF−: the influence of vibration at a transition state

New ab initio potential energy functions for collinear OHF^? and OHF have been used with time-dependent wavepacket studies in a simulation of the photodetachment spectrum of the OHF^? anion. Franck—Condon excitation of OHF^? lies within the transition state region for the bimolecular reaction F + OH ? O + HF on the lowest triplet surface. The branching ratios for fragmentation of the excited OHF are such that the peaks in this spectrum may each be correlated with dissociation to a single vibrational state of the O + HF(v) or OH(v) + F products. The possible influence of vibrational excitation of the anion has been explored also. This is predicted to lead to marked changes in the spectra. Experimental observations of such spectra could be used in refinement of the potential as could an experiment in which the electron kinetic energy is detected in coincidence with the vibrational states of the molecular products or with the kinetic energy of the atomic products. The calculations revealed a number of metastable resonances on the OHF surface, although these are all at higher energies than are relevant to the photodetachment spectrum from the ground state anion.     

Direct measurement of internal energy of fragmented C60

A new experimental approach has been investigated to measure directly the internal energy of fragmented C60. Doubly charged C60{2+*} prepared in collisions H++C60-->H- +C60{2+*} decay by evaporation of C2 units. We have measured the internal energy distribution of the transient C60{2+*} for each decay channel by analyzing the kinetic energy loss of the scattered anion H-. This method offers an experimental opportunity for studying the fragmentation dynamics of more complex systems such as larger clusters and biomolecules under internal energy controlled conditions.     

Transient magnetoviscosity of dilute ferrofluids

The magnetic field induced change in the viscosity of a ferrofluid, commonly known as the magnetoviscous effect and parameterized through the magnetoviscosity, is one of the most interesting and practically relevant aspects of ferrofluid phenomena. Although the steady state behavior of ferrofluids under conditions of applied constant magnetic fields has received considerable attention, comparatively little attention has been given to the transient response of the magnetoviscosity to changes in the applied magnetic field or rate of shear deformation. Such transient response can provide further insight into the dynamics of ferrofluids and find practical application in the design of devices that take advantage of the magnetoviscous effect and inevitably must deal with changes in the applied magnetic field and deformation. In this contribution Brownian dynamics simulations and a simple model based on the ferrohydrodynamics equations are applied to explore the dependence of the transient magnetoviscosity for two cases: (I) a ferrofluid in a constant shear flow wherein the magnetic field is suddenly turned on, and (II) a ferrofluid in a constant magnetic field wherein the shear flow is suddenly started. Both simulations and analysis show that the transient approach to a steady state magnetoviscosity can be either monotonic or oscillatory depending on the relative magnitudes of the applied magnetic field and shear rate.     

How often are chaotic transients in spatially extended ecological systems?

A traditional assumption in quantitative ecology is that the asymptotic state of the model determines what can be observed in the evolution of the system. It is suggested, however, that irregular transient behaviors may be more relevant than the long term behaviors. Here we investigate how often transient dynamics can be expected in spatially extended ecological systems. Our study suggests that although chaotic transient dynamics indeed exist, sustained dynamics may be more prevalent than transient ones due to the high dimensionality of such systems.     

Local proton hopping mechanism in imidazolium-based plastic crystal: an ab initio molecular dynamics study

Protic organic ionic plastic crystals (POIPCs) are promising solid-state proton conductor materials in anhydrous proton exchange membrane fuel cells, due to their mechanical flexibility and high ionic conductivity in the plastic crystal phase. In typical POIPCs, the ions are orientationally disordered while the centers of mass are ordered (positional order) like the crystal phase. The local disorder provides more degrees of freedom for the translational and rotational diffusion of ions, thus enhancing proton conduction either via the vehicle mechanism or the Grotthuss mechanism. Yet the local dynamics and the interactions of the cations and anions during the proton transfer process are far from being fully understood. Here, we performed Car–Parrinello molecular dynamics (CPMD) simulation on the imidazolium methanesulfate ([ImH][CH₃SO₃]) unit cell. By artificially creating one proton hole, we found that a proton can hop directly between the cations. Though the anion is not directly involved in proton hopping, the oxygen atom in the sulfonate group interacts with the proton and has a synergetic motion along with the proton hopping process. This indicates the structural disorder of imidazolium rings and the aid of an anion can facilitate Grotthuss-type proton hopping in imidazolium-based POIPCs.     

Field applied (FMD) computer simulation of the frequency doubled optical Stark effect

It is shown by field applied molecular dynamics computer simulation (FMD) of liquid water that the frequency doubled optical Stark effect is accompanied by novel second order rise transients which have no known counterpart in orientational theory, based on Langevin/Kielich functions. In the statistically stationary, post transient, steady state, correlation function have been computed which are intricately dependent on the frequency of the pump laser. These transients can be obtained experimentally by modifications of optical Stark effect apparatus for measurement on a femtosecond time scale.     

Transient Emission of Three-Level Atoms in a Photonic Crystal with a Pseudogap

We study the transient behaviour of an external field induced transient emission of three-level atomic systems embedded in a photonic crystal with a pseudogap. The expressions for fluorescence spectra and emission dynamics for luminescent materials in the pseudogap are obtained. The properties of the transient gain in the pseudogap are discussed. It shows that the transient emission in the pseudogap can be effectively controlled.     

Transient chaos in optical metamaterials

We investigate the dynamics of light rays in two classes of optical metamaterial systems: (1) time-dependent system with a volcano-shaped, inhomogeneous and isotropic refractive-index distribution, subject to external electromagnetic perturbations and (2) time-independent system consisting of three overlapping or non-overlapping refractive-index distributions. Utilizing a mechanical-optical analogy and coordinate transformation, the wave-propagation problem governed by the Maxwell's equations can be modeled by a set of ordinary differential equations for light rays. We find that transient chaotic dynamics, hyperbolic or nonhyperbolic, are common in optical metamaterial systems. Due to the analogy between light-ray dynamics in metamaterials and the motion of light in matter as described by general relativity, our results reinforce the recent idea that chaos in gravitational systems can be observed and studied in laboratory experiments.     

Correlation between transient decays in wide gap semiconductors: Photoluminescence vs. photocurrent

Recently, we introduced the Thermalization–Recombination (TR) Model to explain the ubiquitous broad subgap photoluminescence bands in wide bandgap semiconductors [M. Niehus, R. Schwarz, Phys. Status Solidi C 3 (2006) 1637]. The model describes the competition between the thermalization and recombination dynamics of excess carriers trapped in localized states distributed exponentially in energy.In this contribution, we confronted the theoretical and qualitative predictions of the TR Model with experimental results of transient photoluminescence (TPL) of pulsed laser deposited (PLD) polycrystalline gallium nitride (GaN) and polycrystalline zinc oxide (ZnO). The TPL results are compared with transient photocurrent (TPC) measurements in order to highlight the relation between TPL and TPC, as well as similarities in the relaxation dynamics of GaN and ZnO.The general features of the transient decays for both materials can be explained within the framework of the TR model, which is shown to offer significant inside into the relaxation dynamics of wide gap semiconductor materials.     

High-energy-density pentazolate salts: CaN_(10) and BaN_(10)

The search for high energy density materials(HEDMs)in polymeric nitrogen compounds has gained considerable attention.Previous theoretical predictions and experiments have revealed that metal ions can be used to stabilize the pentazolate(N-5)anion.In this work,by employing a machine learning-accelerated crystal structure searching method and first-principles calculations,we found that the new pentazolate salts,CaN(10)and BaN(10),are energetically favorable at high pressures.Phonon dispersion calculations reveal that they are quenchable at ambient pressure.Ab initio molecular dynamics simulations verify their dynamic stability at finite temperature.Bader charge and electron localization function illustrates that alkaline earth atoms serve as electron donors,contributing to the stability of N5 rings.Bonding calculations reveal covalent bonds between nitrogen atoms and weak interactions between N5 rings.Similar to other pentazolate salts,these polymeric nitrides have high energy densities of approximately 2.35 kJ/g for CaN(10)and 1.32 kJ/g for BaN(10).The predictions of CaN(10)and BaN(10)structures indicate that these salts are potential candidates for green nitrogen-rich HEDMs.     

Analysis of transient blow-out dynamics in a swirl-stabilized combustor using large-eddy simulations

In the present work, the flame structure and dynamics of a swirl-stabilized methane/air flame near and at blow-out conditions are investigated using large-eddy simulations (LES). To this end, simulations at stable conditions and during a transient blow-out sequence are performed employing a flamelet/progress variable (FPV) model and a thickened flame (TFLES) approach with finite-rate chemistry. Good agreement is obtained for velocities, OH mass fraction profiles, and statistics between LES and measurements at conditions near blow-out. Lift-off height comparisons reveal that the TFLES model predicts a significantly less stable flame compared with the FPV model, which is consistent with the stability limits observed for the two models. Subsequently, transient blow-out simulations are performed and examined. This analysis is guided by employing early warning indicators from dynamical system analysis to identify critical transition points and precursors that trigger the onset of blow-out. It is found that the variance of the integrated heat release is a sensible quantity as an early warning signal in detecting blow-out. Detailed comparisons are then performed between the two models to examine the difference in terms of the blow-out mechanism. The comparison reveals that the different phases of the transient blow-out sequence are qualitatively similar for the two models. However, local extinction phenomena are more significant for the TFLES model, reducing the stabilizing feedback by hot combustion products and leading to a total blow-off time, which is three times shorter compared to FPV.     

The impact of model detail on power grid resilience measures

Extreme events are a challenge to natural as well as man-made systems. For critical infrastructure like power grids, we need to understand their resilience against large disturbances. Recently, new measures of the resilience of dynamical systems have been developed in the complex system literature. Basin stability and survivability respectively assess the asymptotic and transient behavior of a system when subjected to arbitrary, localized but large perturbations in frequency and phase. To employ these methods that assess power grid resilience, we need to choose a certain model detail of the power grid. For the grid topology we considered the Scandinavian grid and an ensemble of power grids generated with a random growth model. So far the most popular model that has been studied is the classical swing equation model for the frequency response of generators and motors. In this paper we study a more sophisticated model of synchronous machines that also takes voltage dynamics into account, and compare it to the previously studied model. This model has been found to give an accurate picture of the long term evolution of synchronous machines in the engineering literature for post fault studies. We find evidence that some stable fix points of the swing equation become unstable when we add voltage dynamics. If this occurs the asymptotic behavior of the system can be dramatically altered, and basin stability estimates obtained with the swing equation can be dramatically wrong. We also find that the survivability does not change significantly when taking the voltage dynamics into account. Further, the limit cycle type asymptotic behaviour is strongly correlated with transient voltages that violate typical operational voltage bounds. Thus, transient voltage bounds are dominated by transient frequency bounds and play no large role for realistic parameters.     

Anomalous diffusion of a polymer chain in an unentangled melt

Contrary to common belief, hydrodynamic interactions in polymer melts are not screened beyond the monomer length and are important in transient regimes. We show that viscoelastic hydrodynamic interactions (VHIs) lead to anomalous dynamics of a tagged chain in an unentangled melt at t相似文献   

利用可见-近红外-中红外超快光谱揭示离子交换法制备的少层MoS2中缺陷介导的载流子动力学

本文结合可见-近红外-中红外瞬态吸收光谱技术对离子交换法制备的少层MoS₂中缺陷介导的载流子动力学进行了详细的解析. 在近红外瞬态吸收光谱中观察到的宽带漂白信号表明少层MoS₂纳米片带隙中分布着大量的缺陷态. 实验结果明确揭示了载流子被缺陷态的快速捕获以及进一步的复合过程,证明带隙中的缺陷态对MoS₂光生载流子动力学过程起着至关重要的作用. 在中红外瞬态吸收光谱中观察到的正信号到负信号的转变进一步证实了在导带下小于0.24 eV处存在被载流子占据的缺陷态. 这些在少层MoS₂纳米片中存在的缺陷态可以作为有效的载流子捕获中心来辅助光生载流子在皮秒时间尺度内完成非辐射复合过程.     

Anomalous energy transfer dynamics due to torsional relaxation in a conjugated polymer

In isolated conjugated polymers two explanations are in discussion for the redshift of the emission on a picosecond time scale-exciton energy transfer (EET) between conjugated segments along the chains and conformational changes of these segments themselves, i.e., torsional relaxation. In order to resolve this question we perform femtosecond time-resolved transient absorption measurements of the energy relaxation of poly[3-(2,5-dioctylphenyl)thiophene] in toluene solution. We show that torsional relaxation can be distinguished from EET by site-selectively exciting low-energy conjugated segments. We present a unified model that integrates EET and torsional dynamics. In particular, comparison to ultrafast depolarization measurements shows that torsional dynamics cannot be neglected when analyzing EET dynamics and furthermore reveals that the exciton extends itself by about 2 monomer units during torsional relaxation.