Direct imaging of transient molecular structures with ultrafast diffraction

Ultrafast electron diffraction (UED) has been developed to study transient structures in complex chemical reactions initiated with femtosecond laser pulses. This direct imaging of reactions was achieved using our third-generation apparatus equipped with an electron pulse (1.07 +/- 0.27 picoseconds) source, a charge-coupled device camera, and a mass spectrometer. Two prototypical gas-phase reactions were studied: the nonconcerted elimination reaction of a haloethane, wherein the structure of the intermediate was determined, and the ring opening of a cyclic hydrocarbon containing no heavy atoms. These results demonstrate the vastly improved sensitivity, resolution, and versatility of UED for studying ultrafast structural dynamics in complex molecular systems.     

Femtosecond dynamics of electron localization at interfaces

The dynamics of two-dimensional small-polaron formation at ultrathin alkane layers on a silver(111) surface have been studied with femtosecond time- and angle-resolved two-photon photoemission spectroscopy. Optical excitation creates interfacial electrons in quasi-free states for motion parallel to the interface. These initially delocalized electrons self-trap as small polarons in a localized state within a few hundred femtoseconds. The localized electrons then decay back to the metal within picoseconds by tunneling through the adlayer potential barrier. The energy dependence of the self-trapping rate has been measured and modeled with a theory analogous to electron transfer theory. This analysis determines the inter- and intramolecular vibrational modes of the overlayer responsible for self-trapping as well as the relaxation energy of the overlayer molecular lattice. These results for a model interface contribute to the fundamental picture of electron behavior in weakly bonded solids and can lead to better understanding of carrier dynamics in many different systems, including organic light-emitting diodes.     

Magnetic field effect on picosecond electron transfer

The recombination dynamics of a transition metal redox system monitored by femtosecond pump-probe spectroscopy are shown to be sensitive to high magnetic fields at times shorter than 10 picoseconds. The effect, based on coherent population beats of different spin states, is quantitatively accounted for and allows direct access to spin relaxation rates far beyond the time resolution of the fastest electron paramagnetic resonance technique. The presence of this ultrafast magnetic field effect helps in understanding complex reaction schemes in transition metal chemistry, which occur in a wide range of fields, such as bioinorganic chemistry and catalysis.     

C60 rotation in the solid state: dynamics of a faceted spherical top

The rotational dynamics of C(60) in the solid state have been investigated with carbon-13 nuclear magnetic resonance ((13)C NMR). The relaxation rate due to chemical shift anisotropy (1/9T1(CSA)(1)) was precisely measured from the magnetic field dependence of T(1), allowing the molecular reorientational correlation time, tau, to be determined. At 283 kelvin, tau = 9.1 picoseconds; with the assumption of diffusional reorientation this implies a rotational diffusion constant D = 1.8 x 10(10) per second. This reorientation time is only three times as long as the calculated tau for free rotation and is shorter than the value measured for C(60) in solution (15.5 picoseconds). Below 260 kelvin a second phase with a much longer reorientation time was observed, consistent with recent reports of an orientational phase transition in solid C(60). In both phases tau showed Arrhenius behavior, with apparent activation energies of 1.4 and 4.2 kilocalories per mole for the high-temperature (rotator) and low-temperature (ratchet) phases, respectively. The results parallel those found for adamantane.     

Light-induced superconductivity in a stripe-ordered cuprate

One of the most intriguing features of some high-temperature cuprate superconductors is the interplay between one-dimensional "striped" spin order and charge order, and superconductivity. We used mid-infrared femtosecond pulses to transform one such stripe-ordered compound, nonsuperconducting La(1.675)Eu(0.2)Sr(0.125)CuO(4), into a transient three-dimensional superconductor. The emergence of coherent interlayer transport was evidenced by the prompt appearance of a Josephson plasma resonance in the c-axis optical properties. An upper limit for the time scale needed to form the superconducting phase is estimated to be 1 to 2 picoseconds, which is significantly faster than expected. This places stringent new constraints on our understanding of stripe order and its relation to superconductivity.     

Electrons in finite-sized water cavities: hydration dynamics observed in real time

We directly observed the hydration dynamics of an excess electron in the finite-sized water clusters of (H2O)n- with n = 15, 20, 25, 30, and 35. We initiated the solvent motion by exciting the hydrated electron in the cluster. By resolving the binding energy of the excess electron in real time with femtosecond resolution, we captured the ultrafast dynamics of the electron in the presolvated ("wet") and hydrated states and obtained, as a function of cluster size, the subsequent relaxation times. The solvation time (300 femtoseconds) after the internal conversion [140 femtoseconds for (H2O)35-] was similar to that of bulk water, indicating the dominant role of the local water structure in the dynamics of hydration. In contrast, the relaxation in other nuclear coordinates was on a much longer time scale (2 to 10 picoseconds) and depended critically on cluster size.     

Electron-Optical Observations on the agr-Transformation in Troilite

The transformation from high to low troilite occurs via a transitional structure. The transformation to this transitional state is continuous, whereas that to the low-temperature form is discontinuous. This illustrates alternative metastable behavior in a system when nucleation of the low-temperature phase may be impeded.     

Vibrational energy transfer across a reverse micelle surfactant layer

In a suspension of reverse micelles, in which the surfactant sodium dioctyl sulfosuccinate (AOT) separates a water nanodroplet from a bulk nonpolar CCl4 phase, ultrafast vibrational spectroscopy was used to study vibrational energy transfer from the nanodroplet through the AOT interfacial monolayer to the surrounding CCl4. Most of the vibrational energy from the nanodroplet was transferred to the polar AOT head group within 1.8 picoseconds and then out to the CCl4 within 10 picoseconds. Vibrational energy pumped directly into the AOT tail resulted in a slower 20- to 40-picosecond transfer of energy to the CCl4.     

Ultrafast vibrational dynamics at water interfaces

Time-resolved sum-frequency vibrational spectroscopy permits the study of hitherto neglected ultrafast vibrational dynamics of neat water interfaces. Measurements on interfacial bonded OH stretch modes revealed relaxation behavior on sub-picosecond time scales in close resemblance to that of bulk water. Vibrational excitation is followed by spectral diffusion, vibrational relaxation, and thermalization in the hydrogen-bonding network. Dephasing of the excitation occurs in 相似文献   

Disk-to-Disk Transfer as the Rate-Limiting Step for Energy Flow in Phycobilisomes

A broadly tunable picosecond laser source and an ultrafast streak camera were used to measure temporally and spectrally resolved emission from intact phycobilisomes and from individual phycobiliproteins as a function of excitation wavelength. Both wild-type and mutant phycobilisomes of the unicellular cyanobacterium Synechocystis 6701 were examined, as well as two biliproteins, R-phycoerythrin (240 kilodaltons, 34 bilins) and allophycocyanin (100 kilodaltons, 6 bilins). Measurements of intact phycobilisomes with known structural differences showed that the addition of an average of 1.6 phycoerythrin disks in the phycobilisome rod increased the overall energy transfer time by 30 +/- 5 picoseconds. In the isolated phycobiliproteins the onset of emission was as prompt as that of a solution of rhodamine B laser dye and was independent of excitation wavelength. This imposes an upper limit of 8 picoseconds (instrument-limited) on the transfer time from "sensitizing" to "fluorescing" chromophores in these biliproteins. These results indicate that disk-to-disk transfer is the slowest energy transfer process in phycobilisomes and, in combination with previous structural analyses, show that with respect to energy transfer the lattice of approximately 625 light-harvesting chromophores in the Synechocystis 6701 wild-type phycobilisome functions as a linear five-point array.     

Femtosecond phase-coherent two-dimensional spectroscopy

Femtosecond phase-coherent two-dimensional (2D) spectroscopy has been experimentally demonstrated as the direct optical analog of 2D nuclear magnetic resonance. An acousto-optic pulse shaper created a collinear three-pulse sequence with well-controlled and variable interpulse delays and phases,which interacted with a model atomic system of rubidium vapor. The desired nonlinear polarization was selected by phase cycling (coadding experimental results obtained with different interpulse phases). This method may enhance our ability to probe the femtosecond structural dynamics of macromolecules.     

Evidence for new sources of NOX in the lower atmosphere

Laboratory studies show that the reaction of short-lived O2(B3Sigmau) molecules (lifetime approximately 10 picoseconds) with N2 and the photodissociation of the N2:O2 dimer produce NOx in the stratosphere at a rate comparable to the oxidation of N2O by O(1D). This finding implies the existence of unidentified NOX sinks in the stratosphere. The NO2 observed in this experiment is isotopically heavy with a large 15N/14N enhancement. However, photodissociation of this NO2 unexpectedly produced NO molecules with a low 15N/14N ratio. The diurnal odd-nitrogen cycle in the stratosphere will be marked by a complex isotope signature that will be imprinted on the halogen and HOX catalytic cycles.     

重庆蚊母树属物种形态分化及种间亲缘关系的分析

在测定重庆市仅有的蚊母树属3物种33个个体的32项形态指标的基础上,通过多种数量分析方法研究了物种形态分化及种间亲缘关系、结果表明：①各物种在个体水平上存在一定程度的形态分化．但分化程度不一;②蚊母树属植物营养器官形态分化较繁殖器官明显,说明繁殖器官受环境影响较小,性状较稳定;②3物种间坚别性状明显．种间界定较为准确;④3物种间亲缘关系存在一定差异,在系统地位上中华蚊母树处于小叶蚊母树和杨梅叶蚊母树之间,与小叶蚊母树亲缘关系较近,而与杨梅叶蚊母树亲缘关系相对较远。     

Intensity Dependence of the Fluorescence Lifetime of in vivo Chlorophyll Excited by a Picosecond Light Pulse

New data on intensity-dependent lifetimes indicate that all previous in vivo fluorescence studies of chlorophyll by picosecond techniquies must be reinterpreted. Anomalously short lifetimes result from high-intensity effects due to exciton-excition annihilation processes. Measurements in Chlorella pyrenoidosa with single-pulse, low-intensity excitation indicate a longer "true" lifetime of 650 +/- 150 picoseconds.     

Control of energy transfer in oriented conjugated polymer-mesoporous silica composites

Nanoscale architecture was used to control energy transfer in semiconducting polymers embedded in the channels of oriented, hexagonal nanoporous silica. Polarized femtosecond spectroscopies show that excitations migrate unidirectionally from aggregated, randomly oriented polymer segments outside the pores to isolated, aligned polymer chains within the pores. Energy migration along the conjugated polymer backbone occurred more slowly than Forster energy transfer between polymer chains. The different intrachain and interchain energy transfer time scales explain the behavior of conjugated polymers in a range of solution environments. The results provide insights for optimizing nanostructured materials for use in optoelectronic devices.     

Structural dynamics of a catalytic monolayer probed by ultrafast 2D IR vibrational echoes

Ultrafast two-dimensional infrared (2D IR) vibrational echo spectroscopy has proven broadly useful for studying molecular dynamics in solutions. Here, we extend the technique to probing the interfacial dynamics and structure of a silica surface-tethered transition metal carbonyl complex--tricarbonyl (1,10-phenanthroline)rhenium chloride--of interest as a photoreduction catalyst. We interpret the data using a theoretical framework devised to separate the roles of structural evolution and excitation transfer in inducing spectral diffusion. The structural dynamics, as reported on by a carbonyl stretch vibration of the surface-bound complex, have a characteristic time of ~150 picoseconds in the absence of solvent, decrease in duration by a factor of three upon addition of chloroform, and decrease another order of magnitude for the bulk solution. Conversely, solvent-complex interactions increase the lifetime of the probed vibration by 160% when solvent is applied to the monolayer.     

塔里木河中游不同生境胡杨种群的结构特征分析

应用“相邻格子法”对塔里木河中游不同生境胡杨种群进行调查,研究不同生境胡杨种群径级结构和空间分布格局。结果表明:1）不同生境下胡杨径阶结构不同,河漫滩生境胡杨幼苗充足,为增长型种群;过渡地带各径阶分布合理,为稳定型种群;而沙地生境径阶≤16 cm的胡杨种群未出现,为衰退型种群。2）河漫滩以及过渡地带生境胡杨种群在5种空间尺度下均处于集群分布;沙地生境总体为随机分布。3种生境下胡杨种群均在5 m×5 m的尺度有较强的聚集性。3）河漫滩、过渡带生境下各个发育阶段均为集群分布,沙地生境随着发育进程,空间分布由聚集分布向随机分布转化。     

Ultrafast hydrogen-bond dynamics in the infrared spectroscopy of water

We investigated rearrangements of the hydrogen-bond network in water by measuring fluctuations in the OH-stretching frequency of HOD in liquid D2O with femtosecond infrared spectroscopy. Using simulations of an atomistic model of water, we relate these frequency fluctuations to intermolecular dynamics. The model reveals that OH frequency shifts arise from changes in the molecular electric field that acts on the proton. At short times, vibrational dephasing reflects an underdamped oscillation of the hydrogen bond with a period of 170 femtoseconds. At longer times, vibrational correlations decay on a 1.2-picosecond time scale because of collective structural reorganizations.     

Polarity transition records and the geomagnetic dynamo

The Parker-Levy approach to reversals of the geomagnetic field predicts meridional transitional paths of the virtual geomagnetic pole (VGP) which pass either through the site of observation or through its antipode, depending upon the site location and the sense of the polarity transition. Comparison with the most detailed transitional VGP path records presently available gives some indication of the above behavior as predicted by the Parker-Levy model. Discrepancies may be due to complexities in the distribution of cyclonic convection cells in the core not considered in the formal mathematical treatment. The predicted variation in transitional field intensity experienced at any given site also is compatible with several reported transition records.