Optical response of Cu clusters in zeolite template

Optical properties of Cu clusters embedded in mordenite are studied experimentally and theoretically. In this work we discuss spectral features of the system at various reduction steps and compare then with the results of spectra obtained within a theoretical model. The model employed consists of Cu clusters embedded in a homogeneous matrix. A second model employed introduced further variation considering a three component system where air or water can be present. The macroscopic dielectric response of the system is obtained within the Maxwell Garnett approximation. In this approach the complex non-local in homogeneous dielectric response of the zeolite+copper system is replaced by an effective homogeneous dielectric function. Metallic clusters can occupy specific available cavities in the zeolite framework. The presence of clusters that are smaller than the cavities in which they reside can lead to an air-Cu or water-Cu interface which allows shifts in surface plasmon resonance energies. As observed experimentally the energy of the main resonance is seen to be insensitive to the filling fraction ratios and highly susceptible to the embedding matrix properties. Reflectance spectra have been obtained which can be explained within this model.     

Static polarizability of small simple metal clusters in dielectric media

Using the local-density-functional method and spherical jellium model, the electronic structure and static polarizability α(0) of small simple metal clusters (Al, Li, Na, K, Rb, and Cs) surrounding by media with dielectric constants ε = 1 ÷ 25 have been calculated. It has been obtained that α(0) of the smallest clusters with a low mean valence electron density is a decreasing function of ε, whereas for the clusters with a high valence electron density it rises with ε.     

Dielectric response of polar liquids in narrow slit pores

Based on molecular dynamics (MD) simulations and a simple (Stockmayer) model we investigate the static and dynamic dielectric response of polar liquids confined to narrow slit pores. The MD simulations are used to calculate the time-dependent polarization fluctuations along directions parallel and perpendicular to the walls, from which the components of the frequency-dependent dielectric tensor can be derived via linear response theory. Our numerical results reveal that the system's response is strongly anisotropic. The parallel dielectric function, epsilonparallel(omega), has Debye-like character very similar to the corresponding isotropic bulk function, epsilonbulk(omega), at the same chemical potential. Indeed, the main confinement effect on epsilonparallel(omega) consists in a shift toward smaller values relative to the bulk function. On the other hand, in the perpendicular direction we observe a characteristic peak in the absorption part of the dielectric function, epsilonperpendicular(omega). This peak is absent in the bulk system and reflects strongly pronounced, damped oscillations in the polarization fluctuations normal to the walls. We discuss two possible origins of the oscillations (and the resulting absorption peak), that is collective oscillations of dipoles in clusters formed parallel to the walls, and the existence of a "dipolaron mode" previously observed in MD simulations of bulk polar fluids.     

Water molecule clusters measured at water/air interfaces using atomic force microscopy

During the tip approach to hydrophobic surfaces like the water/air interface, the measured interaction force reveals a strong attraction with a range of approximately 250 nm at some points along the interface. The range of this force is approximately 100 times larger than the measured for gold (approximately 3 nm) and 10 times larger than the one for hydrophobic silicon surfaces (approximately 25 nm). At other points the interface exerts a medium range repulsive force growing stepwise as the tip approaches the interface plane, consequently the hydrophobic force is a strong function of position. To explain these results we propose a model where the force on the tip is associated with the exchange of a small volume of the interface with a dielectric permittivity epsilon(int) by the tip with a dielectric permittivity epsilon(tip). By assuming a oscillatory spatial dependence for the dielectric permittivity it is possible to fit the measured force profiles. This dielectric spatial variation was associated with the orientation of the water molecules arrangement in the interfacial region. Small nanosized hydrogen-bond connected cages of water molecules present in bulk water at the interface are oriented by the interfacial electric field generated by the water molecules broken bonds, one broken hydrogen bond out of every four. This interfacial field orients small clusters formed by approximately 100 water molecules into larger clusters (approximately 100 nm). In the limit of small (less than 5 nm thick) water molecule cages we have modeled the static dielectric permittivity (epsilon) as the average response of those cages. In these regions the dielectric permittivity for water/air interfaces decreases monotonically from the bulk value epsilon approximately 80 to approximately 2 at the interface. For regions filled with medium size cages, the tip senses the structure of each cage and the static dielectric permittivity is matched to the geometrical features of these cages sized approximately 25 to 40 nm. Interfacial electric energy density values were calculated using the electric field intensity and the dielectric permittivity obtained by the fitting of the experimental points. The integration of the electric energy density along the interfacial region gives a value of 0.072 J m(-2) for interfacial energy density for points where the hydrophobic force has a range of approximately 250 nm. Regions formed by various clusters result in lower values of the interfacial energy density.     

Emergence of the genuine Johari-Goldstein secondary relaxation in m-fluoroaniline after suppression of hydrogen-bond-induced clusters by elevating temperature and pressure

The dielectric spectra of the glass former, m-fluoroaniline (m-FA), at ambient pressure show the presence of a secondary relaxation, which was identified in the literature as the universal Johari-Goldstein (JG) beta relaxation. However, published elastic neutron scattering and simulation data [D. Morineau, C. Alba-Simionesco, M. C. Bellisent-Funel, and M. F. Lauthie, Europhys. Lett. 43, 195 (1998); D. Morineau and C. Alba-Simionesco, J. Chem. Phys. 109, 8494 (1998)] showed the presence of hydrogen-bond-induced clusters of limited size in m-FA at ambient pressure and temperature of the dielectric measurements. The observed secondary relaxation may originate from the hydrogen-bond-induced clusters. If so, it should not be identified with the JG beta relaxation that involves essentially all parts of the molecule and has certain characteristics [K. L. Ngai and M. Paluch, J. Chem. Phys. 120, 857 (2004)], but then arises the question of where is the supposedly universal JG beta relaxation in m-FA. To gain a better understanding and resolving the problem, we perform dielectric measurements at elevated pressures and temperatures to suppress the hydrogen-bond-induced clusters and find significant changes in the dielectric spectra. The secondary relaxation observed at ambient pressure in m-FA is suppressed, indicating that indeed it originates from the hydrogen-bond-induced clusters. The spectra of m-FA are transformed at high temperature and pressure to become similar to that of toluene. The new secondary relaxation that emerges in the spectra has properties of a genuine JG relaxation like in toluene.     

Characterization of large supported metal clusters by optical spectroscopy

Small sodium and silver particles were generated on dielectric substrates like LiF, quartz and sapphire under ultrahigh vacuum conditions. The optical transmission spectra of the clusters were measured as a function of cluster size and shape, for low and high substrate temperatures as well as for s- and p- polarization of the incident light. Excitation of dipolar surface plasmon oscillations in the directions normal and parallel to the substrate surface could be identified. Furthermore, optical spectra for Na and Ag clusters were calculated with the classical Mie theory. The measured spectra vary strongly if the experimental conditions are changed and can be exploited, for example, to characterize the particles with regard to their size and shape. In particular, the axial ratio of the spheroidal clusters could be determined. Its value is considerably different for the two investigated metals and depends on the substrate material. Furthermore, the temperature of the substrate has a pronounced influence on the shape of the particles. At low temperature of T=100 K two-dimensional island growth is predominant. The particles extend only little in the direction perpendicular to the surface and coalesce readily at small coverage of metal atoms. In contrast, the clusters are truly three-dimensional at T=300 K. At this stage, sodium particles still exhibit a rather small axial ratio whereas silver clusters appear almost spherical. Thus, measurements of the optical spectra permit direct in situ monitoring of cluster growth during the nucleation of adsorbed atoms and of temperature induced shape variations. In addition to investigations of the shape of the particles, the quadrupolar surface plasmon mode was observed for Ag clusters.     

Electrorheological properties of suspensions of hollow globular titanium oxide/polypyrrole particles

Hollow globular clusters of titanium oxide (TiO₂) nanoparticles were synthesized by a simple hydrothermal method. The prepared particles were consequently coated by in situ polymerization of conductive polymer polypyrrole (PPy) to obtain novel core–shell structured particles as a dispersed phase in electrorheological (ER) suspensions. The X-ray diffraction analysis and scanning electron microscopy provided information on particle composition and morphology. It appeared that PPy coating improved the compatibility of dispersed particles with silicone oil which results in higher sedimentation stability compared to that of mere TiO₂ particles-based ER suspension. The ER properties were investigated under both steady and oscillatory shears. It was found that TiO₂/PPy particles-based suspension showed higher ER activity than that of mere TiO₂ hollow globular clusters. These observations were elucidated well in view of their dielectric spectra analysis; a larger dielectric loss enhancement and faster interfacial polarization were responsible for a higher ER activity of core–shell structured TiO₂/PPy-based suspensions. Investigation of changes in ER properties of prepared suspensions as a function of particles concentration, viscosity of silicone oil used as a suspension medium, and electric field strength applied was also performed.     

Ground state and response properties of mercury clusters

The change of the cohesive energy and the optical absorption spectra of small singly sized Hg clusters is discussed. The cohesive energy allows one to determine the different regimes of chemical bonding. The optical spectra show an abrupt transition to a collective, plasmon-like absorption as a function of increasing cluster size. The position of the one plasmon peak is: 1) independent of the charge state, 2) nearly independent of cluster size, and 3) agrees with that of the classical Mie plasmon calculated from the experimental dielectric constants. The width of the plasmon peaks is discussed. A strong influence of electronic correlations on the cluster size dependence of the oscillator strength is observed.     

Organofunctional Metal Oxide Clusters as Building Blocks for Inorganic-Organic Hybrid Materials

The controlled hydrolysis of metal alkoxides in the presence of methacrylic acid results in metal oxide clusters capped by polymerizable methacrylate ligands. Radical polymerization of small portions of such clusters with organic co-monomers allows the preparation of an interesting new type of inorganic-organic hybrid polymers in which the metal oxo clusters efficiently crosslink the organic polymers chains. SAXS investigations revealed that the clusters may aggregate to form clusters of clusters. The properties of the hybrid materials, such as thermal stability, swelling, dielectric and mechanical properties, depend not only on the portion of incorporated cluster, i.e. the crosslinking density, but also on the kind of employed cluster.     

Polyimides reinforced with the sol‐gel derived organosilicon nanophase as low dielectric permittivity materials

Polyimide (PI) nanocomposites prepared by the in situ generation of crosslinked organosilicon nanophase (ON) through the sol‐gel process were characterized by densities, thermally stimulated depolarization currents and dielectric relaxation spectroscopy. Both a looser molecular packing of PI chain fragments adjacent to the ON and a loose inner structure of the spatial aggregates of ON were assumed to be responsible for a non‐additive decrease of the experimental values of dielectric permittivity for the nanocomposites. The pattern of composition dependence of the apparent dielectric permittivity of the ON suggested a probability of a morphological change around the composition PAAS/MTS = 100/16 (presumably, a sort of percolation transition from small‐size, individual clusters into large‐size, infinite clusters). Thus, PI reinforced with the sol‐gel derived nanophase may have a reasonably good potential as low dielectric permittivity materials. Copyright © 2004 John Wiley & Sons, Ltd.     

Ionization potentials of large sodium doped ammonia clusters

In a continuous neat supersonic expansion ammonia clusters are generated and doped with sodium atoms in a pickup cell. Thus clusters of the form Na(NH(3))(n) are produced that are photoionized by a tunable dye laser system. The ions are mass analyzed in a reflectron time-of-flight mass spectrometer, and the wavelength dependent ion signals serve for the determination of the ionization potentials (IP) of the different clusters in the size range 10< or =n< or =1500. Aside from a plateau for 10< or =n< or =17 and smaller steps at n=24, 35, and 59 on the average a continuous decrease of the IP with cluster size is observed. The IPs in this size range are linear with (n+1)(-13) and extrapolate to IP(n=infinity)=1.66+/-0.01 eV. The slope is consistent with a dielectric continuum model of the solvated electron and the dielectric constant of the solid. The extrapolated IPs are compared with results obtained for negative ammonia cluster ions and metallic solutions in liquid ammonia. Differences are explained by the presence of counterions and their various distances from the solvated electron.     

Effects of nonionic surfactant C12E5 on the cooperative dynamics of water

A dielectric relaxation study of binary mixtures of nonionic surfactant C12E5 + water has been made as a function of temperature in the isotropic micellar, lamellar, and hexagonal regions of the phase diagram. Two dielectric dispersion steps were found and could be assigned to the intermolecular cooperative dynamics of water at the micellar interface and in the bulk water domains. A quantitative analysis is given. The relaxation amplitudes were used to determine effective hydration numbers. The activation energies of water relaxation were calculated from the relaxation times. The data indicate weaker surfactant-water and water-water interactions near the micellar interface compared to those of bulk liquid water. Further analysis revealed the presence of water clusters large enough to show a cooperative relaxation mode even at high surfactant concentrations. However, the relaxation time of this mode is larger compared to that of pure water. This points out the importance of confinement effects on water dynamics.     

Some dielectric solvation effects on the energetics of electrified metal interfaces and related molecular systems

The sensitivity of the surface potential of metal-vacuum interfaces to the presence of molecular dielectric (solvating) species both with or without free ionic/electronic charge is discussed with the objective of comparing the behavior of such “electrified dielectric” interfaces with analogous metal-solution (i.e. electrochemical) systems. The close connection between “surface-potential” scales based on work function (Φ) and electrode-potential (E) measurements is outlined. The chief factors determining the surface potential are illustrated by means of composition-dependent Φ data for single-crystal metal surfaces modified by thin (1–3 monolayer) films of dipolar molecules along with ionizable species in relation to E values for corresponding in-situ electrochemical interfaces. The former Φ-composition measurements, for vacuum-based electrified dielectric interfaces, demonstrate how even primary solvation (i.e. a single molecular layer) is sufficient to engender substantial and electrochemical-like stabilization of interfacial ionic species. The essential nature of dielectric-induced modifications to electron-transfer energetics at metal-vacuum interfaces are considered, and also related to the observed marked solvation effects on the charging of metalliclike clusters, such as fullerenes. The potential value of such unified treatments of surface potential-charge relationships in vacuum and electrochemical systems is also sketched in more general terms.     

Hydrogen bonded clusters of alcohol molecules in inert solvents: a chain statistics approach

A theory is proposed for modeling the autoassociation of alcohol molecules either in the neat liquid or in inert (non-complexing) solvents. This autoassociation by hydrogen bonds takes the form of clusters which can be predominantly open or cyclized chains, depending on the concentration. Chain conformation statistics are used for calculating the dipole moment of each type of chain. Cyclization equilibrium theory is employed for obtaining formulae for the fraction of all types of clusters. The total Kirkwood angular correlation factorg is calculated in function of the concentration. For this only two parameters are used; the first one is a common equilibrium constant for H bond dissociation; the second one is closely linked to the stiffness of the chains. A numerical illustration is presented for the case of normal hexanol in various aliphatic solvents, for which several dielectric data exist in the literature.     

A mean field analysis of the static dielectric behavior of linear lower alcohols

The static dielectric responses of methanol, ethanol, and 1-propanol up to 1-hexanol are discussed in terms of a stiff-chain lattice model for the alcohol clusters. An analytical expression for the Kirkwood correlation factor gK is derived in terms of the canonical partition function associated to the configurational statistics of any of the dimers building up a chain. This allows for the estimate of the dipole moment mu0 of an alcohol molecule in the liquid phase from the temperature dependence of the dielectric constant. All alcohol species appear to be characterized by a dipole moment larger than in the vapor phase. The Kirkwood correlation factor is found to be an increasing function of the alkyl tail length.     

Models for the description of the H3O+ and OH− ions in water

Structures of the H₃O⁺-OH ion pair surrounded by up to three water molecules have been studied. Since the ion-pair structure is always above the corresponding neutral water structure, a constrained geometry optimization is needed. The energy difference between the ion-pair structure and the neutral water structure is studied as a function of the number of surrounding water molecules. The effect of the surrounding water solvent is also studied by placing the model system in a spherical cavity in a dielectric medium. The main results are that the energy difference stabilizes at 10–20 kcal/mol for the larger clusters and that an effect indicating a mechanism for charge separation can be noticed on the geometries of these clusters. Results obtained using gradient-corrected density-functional theory are compared to a configuration interaction treatment using a scaling procedure of the correlation energy. © 1996 by John Wiley & Sons, Inc.     

Hydration Dynamics of Water near an Amphiphilic Model Peptide at Low Hydration Levels: A Dielectric Relaxation Study

A dielectric relaxation study of aqueous solutions of the amphiphilic model peptide N‐acetyl‐leucine amide (NALA) at 298 K over a wide range of hydration levels is presented. The experiments range from states where water builds up several hydration layers to states where single water molecules or small water clusters are shared by several NALA molecules. The dielectric spectra reveal two modes on the 10 and 100 ps timescales. These are largely broadened with regard to the Lorentzian shape caused by simple Debye‐type relaxation, and are well described by the Kohlrausch–Williams–Watts stretched exponential function. The fast mode is assigned to water reorientation comprising bulk water as well as hydration water. Even when all water molecules are in contact with the solute, this fast component is dominant, and its mean relaxation time is retarded by less than a factor of two relative to neat water. The amplitude of the slow process is far higher than expected for the dipolar reorientation of the solute. The observations are consistent with results from molecular dynamics simulations for a similar model peptide reported in the literature. They suggest that the slow relaxation mode is mainly founded in peptide–water dipolar couplings, with some additional contribution from slowly reorienting hydration water molecules. The results are discussed with regard to the hydration dynamics of proteins and the interpretation of dielectric spectra of protein solutions.     

Binary clusters: homogeneous alloys and nucleus-shell structures

Extinction spectra of Ag_x-Au_(1?x)-alloy particles embedded in glass are compared to spectra of gold coated silver clusters and silver coated gold clusters. It is shown, that the optical extinction of alloy particles is described by the Mie theory applying the homogeneous dielectric function \(\hat \varepsilon \) (ω,R, x) measured by Paquet. The absorption of core-shell clusters was calculated deriving an extension of the Mie theory to spheres with arbitrary numbers of shells of arbitrary materials. Comparison to measured spectra points to s-electron motion in the clusters with only slight scattering at the interior interface. The appearance of two distinct Mie peaks however proves the existence of the sharp Ag-Au interface. The extended Mie formalism was also applied to a multilayer system consisting of sodium and a dielectric substance as an example for a spherical hetero structure.     

Monte-Carlo simulation of water solvent with biomolecules: Serines with reaction-field correction

Along the lines of previous work [S. Romano and E. Clementi, Gazz. Chim. Ital. 108 , 319 (1978); Int. J. Quantum Chem. 14 , 839 (1978); 17 , 1007 (1980)], we carried out Monte Carlo simulation on serine–water clusters (the neutral molecule and two conformers of the zwitterion) surrounded by an appropriate dielectric continuum simulating the bulk solvent. Results for clusters in vacuo and in the dielectric continuum were compared; similarities and differences could be qualitatively interpreted as produced by competition among different factors.     

Frequency and field dependent conductivity in Pd-based metal cluster compounds

Ligand stabilized metal cluster compounds and colloids consist of nanometer-size metal cores surrounded by ligand shells. We study the dielectric properties of randomly packed aggregates of these compounds as a function of temperature T, electric field E and frequency ω. Cores were formed by Pd-atoms and stabilized by a selection of ligands. The core size varied between 2.4 and 3.6 nm (monodisperse) and 18 nm (5–10% dispersion). The dielectric properties of all compounds show scaling: the same functional dependence of the normalized conductivity on normalized frequency irrespective of temperature. The results imply that at room temperature at all frequencies below 1 THz exclusively hopping between the particles is seen. More details of the hopping processes are obtained by varying E. The observed dependences are consistent with stochastic models that use random packing of clusters inside the sample.