Hydrated electron dynamics: from clusters to bulk

The electronic relaxation dynamics of size-selected (H2O)n-/(D2O)n[25 eaq-(s(dagger)) internal conversion lifetime.     

Observation of large water-cluster anions with surface-bound excess electrons

Anionic water clusters have long been studied to infer properties of the bulk hydrated electron. We used photoelectron imaging to characterize a class of (H2O)n- and (D2O)n- cluster anions (n 相似文献   

Electron solvation in finite systems: femtosecond dynamics of iodide. (Water)n anion clusters

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.     

Wet electrons at the H2O/TiO2(110) surface

At interfaces of metal oxide and water, partially hydrated or "wet-electron" states represent the lowest energy pathway for electron transfer. We studied the photoinduced electron transfer at the H2O/TiO2(110) interface by means of time-resolved two-photon photoemission spectroscopy and electronic structure theory. At approximately 1-monolayer coverage of water on partially hydroxylated TiO2 surfaces, we found an unoccupied electronic state 2.4 electron volts above the Fermi level. Density functional theory shows this to be a wet-electron state analogous to that reported in water clusters and which is distinct from hydrated electrons observed on water-covered metal surfaces. The decay of electrons from the wet-electron state to the conduction band of TiO2 occurs in 相似文献   

Characterization of excess electrons in water-cluster anions by quantum simulations

Water-cluster anions can serve as a bridge to understand the transition from gaseous species to the bulk hydrated electron. However, debate continues regarding how the excess electron is bound in (H2O)-n, as an interior, bulklike, or surface electronic state. To address the uncertainty, the properties of (H2O)-n clusters with 20 to 200 water molecules have been evaluated by mixed quantum-classical simulations. The theory reproduces every observed energetic, spectral, and structural trend with cluster size that is seen in experimental photoelectron and optical absorption spectra. More important, surface states and interior states each manifest a characteristic signature in the simulation data. The results strongly support assignment of surface-bound electronic states to the water-cluster anions in published experimental studies thus far.     

How do small water clusters bind an excess electron?

The arrangement of water molecules around a hydrated electron has eluded explanation for more than 40 years. Here we report sharp vibrational bands for small gas-phase water cluster anions, (H2O)(4-6)- and (D2O)(4-6)-. Analysis of these bands reveals a detailed picture of the diffuse electron-binding site. The electron is closely associated with a single water molecule attached to the supporting network through a double H-bond acceptor motif. The local OH stretching bands of this molecule are dramatically distorted in the pentamer and smaller clusters because the excited vibrational levels are strongly coupled to the electron continuum. The vibration-to-electronic energy transfer rates, as revealed by line shape analysis, are mode-specific and remarkably fast, with the symmetric stretching mode surviving for less than 10 vibrational periods [50 fs in (H2O)4-].     

Isolating the spectroscopic signature of a hydration shell with the use of clusters: superoxide tetrahydrate

Cluster spectroscopy, aided by ab initio theory, was used to determine the detailed structure of a complete hydration shell around an anion. Infrared spectra of size-selected O(2)-. (H(2)O)(n) (n = 1 to 4) cluster ions were obtained by photoevaporation of an argon nanomatrix. Four water molecules are required to complete the coordination shell. The simple spectrum of the tetrahydrate reveals a structure in which each water molecule is engaged in a single hydrogen bond to one of the four lobes of the pi* orbital of the superoxide, whereas the water molecules bind together in pairs. This illustrates how water networks deform upon accommodating a solute ion to create a distinct supramolecular species.     

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   

Femtosecond Dynamics of Excited-State Evolution in

Time-resolved absorption spectroscopy on the femtosecond time scale has been used to monitor the earliest events associated with excited-state relaxation in tris-(2,2'-bipyridine)ruthenium(II). The data reveal dynamics associated with the temporal evolution of the Franck-Condon state to the lowest energy excited state of this molecule. The process is essentially complete in approximately 300 femtoseconds after the initial excitation. This result is discussed with regard to reformulating long-held notions about excited-state relaxation, as well as its implication for the importance of non-equilibrium excited-state processes in understanding and designing molecular-based electron transfer, artificial photosynthetic, and photovoltaic assemblies in which compounds of this class are currently playing a key role.     

Size-Specific Infrared Spectra of Benzene-(H2O)n Clusters (n = 1 through 7): Evidence for Noncyclic (H2O)n Structures

Resonant ion-dip infrared spectroscopy has been used to record size-specific infrared spectra of C(6)H(6)-(H(2)O)n clusters with n = 1 through 7 in the O-H stretch region. The O-H stretch spectra show a dramatic dependence on cluster size. For the n = 3 to 5 clusters, the transitions can be divided into three types-attributable to free, pi hydrogen-bonded, and single donor water-water O-H stretches-consistent with a C(6)H(6)-(H(2)O)n structure in which benzene is on the surface of a cyclic (H(2)O)n cluster. In n = 6 and 7 clusters, the spectra show distinct new transitions in the 3500 to 3600 wave number region. After comparison of these results with the predictions of ab initio calculations on (H(2)O)n clusters, these new transitions have been assigned to double donor O-H stretches associated with the formation of a more compact, noncyclic structure beginning with (H(2)O)(6). This is the same size cluster for which ab initio calculations predict that a changeover to noncyclic (H(2)O)n structures will occur.     

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.     

Boron-Oxygen Polyanion in the Crystal Structure of Tunellite

The crystal structure of tunellite, SrO.3B(2)O(3).4H(2)O, with infinite sheets of composition n[B(6)O(9)(OH)(2)](2-), has cations and water molecules in the spaces within the sheets. Adjacent sheets are held together by hydrogen bonding through the water molecules. The boron-oxygen polyanions provide the first example in hydrated borate crystals of one oxygen linked to three borons.     

Infrared signature of structures associated with the H+(H2O)n (n = 6 to 27) clusters

We report the OH stretching vibrational spectra of size-selected H+(H2O)n clusters through the region of the pronounced "magic number" at n = 21 in the cluster distribution. Sharp features are observed in the spectra and assigned to excitation of the dangling OH groups throughout the size range 6 相似文献   

Solvent tuning of electrochemical potentials in the active sites of HiPIP versus ferredoxin

A persistent puzzle in the field of biological electron transfer is the conserved iron-sulfur cluster motif in both high potential iron-sulfur protein (HiPIP) and ferredoxin (Fd) active sites. Despite this structural similarity, HiPIPs react oxidatively at physiological potentials, whereas Fds are reduced. Sulfur K-edge x-ray absorption spectroscopy uncovers the substantial influence of hydration on this variation in reactivity. Fe-S covalency is much lower in natively hydrated Fd active sites than in HiPIPs but increases upon water removal; similarly, HiPIP covalency decreases when unfolding exposes an otherwise hydrophobically shielded active site to water. Studies on model compounds and accompanying density functional theory calculations support a correlation of Fe-S covalency with ease of oxidation and therefore suggest that hydration accounts for most of the difference between Fd and HiPIP reduction potentials.     

Infrared spectroscopic evidence for protonated water clusters forming nanoscale cages

Size-dependent development of the hydrogen bond network structure in large sized clusters of protonated water, H+(H2O)n (n = 4 to 27), was probed by infrared spectroscopy of OH stretches. Spectral changes with cluster size demonstrate that the chain structures at small sizes (n less, similar 10) develop into two-dimensional net structures (approximately 10 < n < 21), and then into nanometer-scaled cages (n >/= 21).     

Dynamics of hydrogen bromide dissolution in the ground and excited states

The dissolution of acids is one of the most fundamental solvation processes, and an important issue is the nature of the hydration complex resulting in ion pair formation. We used femtosecond pump-probe spectroscopy to show that five water molecules are necessary for complete dissolution of a hydrogen bromide molecule to form the contact ion pair H+.Br-(H2O)n in the electronic ground state. In smaller mixed clusters (n < 5), the ion pair formation can be photoinduced by electronic excitation.     

Time-resolved investigation of coherently controlled electric currents at a metal surface

Studies of current dynamics in solids have been hindered by insufficiently brief trigger signals and electronic detection speeds. By combining a coherent control scheme with photoelectron spectroscopy, we generated and detected lateral electron currents at a metal surface on a femtosecond time scale with a contact-free experimental setup. We used coherent optical excitation at the light frequencies omega(a) and omega(a)/2 to induce the current, whose direction was controlled by the relative phase between the phase-locked laser excitation pulses. Time- and angle-resolved photoelectron spectroscopy afforded a direct image of the momentum distribution of the excited electrons as a function of time. For the first (n = 1) image-potential state of Cu(100), we found a decay time of 10 femtoseconds, attributable to electron scattering with steps and surface defects.     

Spectroscopic determination of the OH- solvation shell in the OH-.(H2O)n clusters

There has been long-standing uncertainty about the number of water molecules in the primary coordination environment of the OH- and F- ions in aqueous chemistry. We report the vibrational spectra of the OH-.(H2O)n and F-.(H2O)n clusters and interpret the pattern of OH stretching fundamentals with ab initio calculations. The spectra of the cold complexes are obtained by first attaching weakly bound argon atoms to the clusters and then monitoring the photoinduced evaporation of these atoms when an infrared laser is tuned to a vibrational resonance. The small clusters (n 相似文献   

H2O2对褐蘑菇膳食纤维脱色效果研究

为了改善褐蘑菇膳食纤维色泽,提高产品质量,以过氧化氢为脱色剂采用正交试验方法进行褐蘑菇膳食纤维的氧化脱色研究,探讨过氧化氢浓度、脱色时间、料液比对褐蘑菇膳食纤维脱色效果的影响。结果表明:褐蘑菇膳食纤维脱色的最佳工艺为H2O2浓度5%、脱色时间4h、料液比1∶7。脱色后,褐蘑菇膳食纤维的膨胀力、持水力和结合水力明显提高。