共查询到20条相似文献，搜索用时 500 毫秒
1.
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. 相似文献
2.
Electron solvation dynamics in photoexcited anion clusters of I-(D2O)n=4-6 and I-(H2O)4-6 were probed by using femtosecond photoelectron spectroscopy (FPES). An ultrafast pump pulse excited the anion to the cluster analog of the charge-transfer-to-solvent state seen for I- in aqueous solution. Evolution of this state was monitored by time-resolved photoelectron spectroscopy using an ultrafast probe pulse. The excited n = 4 clusters showed simple population decay, but in the n = 5 and 6 clusters the solvent molecules rearranged to stabilize and localize the excess electron, showing characteristics associated with electron solvation dynamics in bulk water. Comparison of the FPES of I-(D2O)n with I-(H2O)n indicates more rapid solvation in the H2O clusters. 相似文献
3.
Fecko CJ Eaves JD Loparo JJ Tokmakoff A Geissler PL 《Science (New York, N.Y.)》2003,301(5640):1698-1702
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. 相似文献
4.
The proton transfer mechanism between aqueous Br?nsted acids and bases, forming an encounter pair, has been studied in real time with ultrafast infrared spectroscopy. The transient intermediacy of a hydrated proton, formed by ultrafast dissociation from an optically triggered photoacid proton donor ROH, is implicated by the appearance of an infrared absorption marker band before protonation of the base, B-. Thus, proton exchange between an acid and a base in aqueous solution is shown to proceed by a sequential, von Grotthuss-type, proton-hopping mechanism through water bridges. The spectra suggest a hydronium cation H3O+ structure for the intermediate, stabilized in the Eigen configuration in the ionic complex RO-...H3O+...B-. 相似文献
5.
Liu T Langston ML Li D Pigga JM Pichon C Todea AM Müller A 《Science (New York, N.Y.)》2011,331(6024):1590-1592
We report a self-recognition phenomenon based on an assembly process in a homogeneous dilute aqueous solution of two nano-scaled, spherical polyprotic metal oxide-based macroions (neutral species in crystals), also called Keplerates of the type [(linker)??(pentagon)??]≡[{M(H?O)}??{(Mo)Mo?}??] where M is Fe(III) or Cr(III). Upon deprotonation of the neutral species, the resulting macroions assemble into hollow "blackberry"-type structures through very slow homogeneous dimer-oligomerization processes. Although the geometrical surface structures of the two macroions are practically identical, mixtures of these form homogeneous superstructures, rather than mixed species. The phase separation is based on the difference in macroionic charge densities present during the slow homogeneous dimer or oligomer formation. The surface water ligands' residence times of Cr(III) and Fe(III) differ markedly and lead to very different interfacial water mobilities between the Keplerates. 相似文献
6.
P Gilch F Pollinger-Dammer C Musewald ME Michel-Beyerle UE Steiner 《Science (New York, N.Y.)》1998,281(5379):982-984
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. 相似文献
7.
Bragg AE Verlet JR Kammrath A Cheshnovsky O Neumark DM 《Science (New York, N.Y.)》2004,306(5696):669-671
The electronic relaxation dynamics of size-selected (H2O)n-/(D2O)n[25 eaq-(s(dagger)) internal conversion lifetime. 相似文献
8.
The intermediate structures formed through radiationless transitions are termed "dark" because their existence is inferred indirectly from radiative transitions. We used ultrafast electron diffraction to directly determine these transient structures on both ground-state and excited-state potential energy surfaces of several aromatic molecules. The resolution in space and time (0.01 angstrom and 1 picosecond) enables differentiation between competing nonradiative pathways of bond breaking, vibronic coupling, and spin transition. For the systems reported here, the results reveal unexpected dynamical behavior. The observed ring opening of the structure depends on molecular substituents. This, together with the parallel bifurcation into physical and chemical channels, redefines structural dynamics of the energy landscape in radiationless processes. 相似文献
9.
Pérez C Muckle MT Zaleski DP Seifert NA Temelso B Shields GC Kisiel Z Pate BH 《Science (New York, N.Y.)》2012,336(6083):897-901
Theory predicts the water hexamer to be the smallest water cluster with a three-dimensional hydrogen-bonding network as its minimum energy structure. There are several possible low-energy isomers, and calculations with different methods and basis sets assign them different relative stabilities. Previous experimental work has provided evidence for the cage, book, and cyclic isomers, but no experiment has identified multiple coexisting structures. Here, we report that broadband rotational spectroscopy in a pulsed supersonic expansion unambiguously identifies all three isomers; we determined their oxygen framework structures by means of oxygen-18-substituted water (H(2)(18)O). Relative isomer populations at different expansion conditions establish that the cage isomer is the minimum energy structure. Rotational spectra consistent with predicted heptamer and nonamer structures have also been identified. 相似文献
10.
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
11.
Ihee H Lobastov VA Gomez UM Goodson BM Srinivasan R Ruan CY Zewail AH 《Science (New York, N.Y.)》2001,291(5503):458-462
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. 相似文献
12.
通过水工模型实验,将阶梯坝面消能运用于水利工程的泄水建筑物上,以改善其水力条件,增加泄流面消能、减少下泄水流动量和速度,减轻泄水建筑物下游消能负担、减小(或省免) 下游消能设施及工程量,增强泄水建筑物(如溢洪道) 的整体稳定和安全。这项消能技术多次在云南省的水利工程中运用,取得了较好的效益。 相似文献
13.
Wörner HJ Bertrand JB Fabre B Higuet J Ruf H Dubrouil A Patchkovskii S Spanner M Mairesse Y Blanchet V Mével E Constant E Corkum PB Villeneuve DM 《Science (New York, N.Y.)》2011,334(6053):208-212
Conical intersections play a crucial role in the chemistry of most polyatomic molecules, ranging from the simplest bimolecular reactions to the photostability of DNA. The real-time study of the associated electronic dynamics poses a major challenge to the latest techniques of ultrafast measurement. We show that high-harmonic spectroscopy reveals oscillations in the electronic character that occur in nitrogen dioxide when a photoexcited wave packet crosses a conical intersection. At longer delays, we observe the onset of statistical dissociation dynamics. The present results demonstrate that high-harmonic spectroscopy could become a powerful tool to highlight electronic dynamics occurring along nonadiabatic chemical reaction pathways. 相似文献
14.
分析紫外光照射下木荷产生自由基的规律和表面化学组成及结构的变化。利用电子自旋共振波谱(ESR)和X射线光电子能谱(XPS)技术分别测量紫外光辐照后木荷颗粒的自由基波谱和X射线光电子能谱。结果表明,木荷自由基的光谱分裂因子g=2.003 3,自由基的强度随着辐照时间按Y=1-e-biPt规律增加,紫外光辐照60 min后,木荷表面氧、碳原子比稍有增加,C—C、C—H和C—O含量增加,C=O含量减少,—O—C=O含量增加为原来的2倍左右,说明木荷表面生成了一些含氧官能团或碳的氧化态增高。 相似文献
15.
A brief review is given of the structures of an important class of reactive intermediates, divalent carbon species (carbenes). The electronic properties of carbenes force an unusual electronic character upon these species that, in turn, leads to intriguing physical and chemical properties. Because of the fleeting nature of carbenes, which are extraordinarily reactive, direct investigation of their structural and chemical behavior has presented a challenge to the experimentalist. The application of spectroscopic and ultrafast laser techniques has met this challenge. With the use of laser methods, along with conventional techniques, quantitative evaluation of the energetics, dynamics, and reactivities of a variety of carbenes has been possible. 相似文献
16.
Ion imaging reveals distinct photodissociation dynamics for propanal cations initially prepared in either the cis or gauche conformation, even though these isomers differ only slightly in energy and face a small interconversion barrier. The product kinetic energy distributions for the hydrogen atom elimination channels are bimodal, and the two peaks are readily assigned to propanoyl cation or hydroxyallyl cation coproducts. Ab initio multiple spawning dynamical calculations suggest that distinct ultrafast dynamics in the excited state deposit each conformer in isolated regions of the ground-state potential energy surface, and, from these distinct regions, conformer interconversion does not effectively compete with dissociation. 相似文献
17.
Protein hydration in aqueous solution 总被引：25，自引：0，他引：25
High-resolution proton nuclear magnetic resonance studies of protein hydration in aqueous solution show that there are two qualitatively different types of hydration sites. A well-defined, small number of water molecules in the interior of the protein are in identical locations in the crystal structure and in solution, and their residence times are in the range from about 10(-2) to 10(-8) second. Hydration of the protein surface in solution is by water molecules with residence times in the subnanosecond range, even when they are located in hydration sites that contain well-ordered water in the x-ray structures of protein single crystals. 相似文献
18.
Bokor J 《Science (New York, N.Y.)》1989,246(4934):1130-1134
A variety of important dynamical phenomena at metal and semiconductor surfaces are now being investigated with the use of new ultrafast measurement techniques involving lasers and nonlinear optics. Understanding of the rates and mechanisms for relaxation of optical excitations of the surface itself as well as those of adsorbates on the surface is providing new insight into surface chemistry, surface phase transitions, and surface recombination of charge carriers in semiconductors. 相似文献
19.
金鱼藻叶表的形态及其对悬浮物的吸附 总被引：1，自引：0，他引：1
通过对金鱼藻形态结构及其对水中悬浮物吸附能力的研究,结果表明：金鱼藻可以吸附水中大量的悬浮物,吸附量可达自身重量的1.58～1.86倍,有利于提高水体的透明度。从叶片表面的形态结构,揭示了金鱼藻吸附悬浮物原因。 相似文献
20.
Recent and subfossil calcareous structures resembling cystose and subclathrate Paleozoic stromatoporoids have been discovered in a sea-linked, stratified, alkaline crater lake on Satonda Island, Indonesia. The structures are produced by mats of coccoid cyanobacteria growing along the lakeshore from the water surface down to the O(2)-H(2)S interface located at a depth of 22.8 meters. Calcification of the mats is controlled by seasonal changes in calcium carbonate supersaturation in the epilimnion. The internally complex structures are a product of two different calcification processes: (i) periodic in vivo calcification of the surficial cyanobacterial layers by low-Mg calcite, and (ii) early postmortem calcification of the cyanobacterial aggregates below the mat surface by microbially precipitated aragonite. The finding supports the idea that Paleozoic stromatoporoids represent fossilized cyanobacteria (stromatolites). It also implies that the stromatoporoid-generating epicontinental seas during the early Paleozoic may have been more alkaline and had a higher carbonate mineral supersaturation than modern seawater. 相似文献