Nonharmonic transverse vibration of the H-bonded molecules and the THz spectra in ice and water

A nonlinear equation of motion is found for the dimer comprising two charged H2O molecules. The THz dielectric response to nonharmonic vibration of a nonrigid dipole, forming the hydrogen bond (HB), is found in the direction transverse to this bond. An explicit expression is derived for the autocorrelator that governs the spectrum generated by transverse vibration (TV) of such a dipole. This expression is obtained by analytical solution of the truncated set of recurrence equations. The far infrared (FIR) spectra of ice at the temperature - 7 degrees C are calculated. The wideband, in the wavenumber (frequency) v range 0... 100.0 cm(-1), spectra are obtained for liquid water at room temperature and for supercooled water at -5.6 degrees C. All spectra are represented in terms of the complex permittivity epsilon(v) and the absorption coefficient alpha(v). The obtained analytical formula for epsilon comprises the term epsilon(perpendicular to) pertinent to the studied TV mechanism with three additional terms Delta epsilon(q), Delta epsilon(mu), and epsilon(or) arising, respectively, from: elastic harmonic vibration of charged molecules along the H-bond; elastic reorientation of HB permanent dipoles; and rather free libration of permanent dipoles in 'defects' of water/ice structure. The suggested TV-dielectric relaxation mechanism allows us: (a) to remove the THz 'deficit' of loss epsilon" inherent in previous theoretical studies; (b) to explain the THz loss and absorption spectra in supercooled (SC) water; and (c) to describe, in agreement with the experiment, the low- and high-frequency tails of the two bands of ice H2O located in the range 10...300 cm(-1). Specific THz dielectric properties of SC water are ascribed to association of water molecules, revealed in our study by transverse vibration of HB charged molecules. (C) 2006 Published by Elsevier B.V.

Anisotropic optical properties of arrays of gold nanorods embedded in alumina

A series of thin films comprising gold nanorods embedded in an alumina matrix have been fabricated with lengths ranging from 75 to 330 nm. Their optical properties, expressed in terms of extinction - In(T), where T is optical transmittance, have been measured as a function of wavelength, rod length, angle of incidence, and incident polarization state. The results are compared to a Maxwell-Garnett based theory modified to take into account the strongly anisotropic nature of the medium. Transverse and longitudinal plasmon resonances are observed. The interaction between the nanorods leads to the splitting of the longitudinal resonance with the longer-wavelength resonance being forbidden for direct optical observations. The shorter-wavelength resonance related to the symmetric coupling between longitudinal plasma excitations in the nanorods depends on rod length, polarization state, and angle of incidence of the probing light. The impact of electron confinement on the optical properties of the gold rods is also seen and may be incorporated into the Maxwell-Garnett theory by restricting the mean free path of the conduction electrons to produce excellent agreement between observations and the complete theory. Annealing experiments that modify the physical structure of the gold confirm this conclusion.

Enhancement of dielectric constant and associated coupling of polarization behavior in thin film relaxor superlattices

Thin film capacitor structures in which the dielectric is composed of superlattices of the relaxors [0.2Pb(Zn1/3Nb2/3)O- 3-0.8BaTiO(3)] and Pb(Mg1/3Nb2/3)O-3 have been fabricated by pulsed laser deposition. Superlattice wavelength (Lambda) was varied between similar to3 and similar to 600 nm, and dielectric properties were investigated as a function of Lambda. Progressive enhancement of the dielectric constant was observed on decreasing Lambda, and, in contrast to previous work, this was not associated with the onset of Maxwell-Wagner behavior. Polarization measurements as a function of temperature suggested that the observed enhancement in dielectric constant was associated with the onset of a coupled response. The superlattice wavelength (Lambda =20 nm) at which coupled functional behavior became apparent is comparable to that found in literature for the onset of coupled structural behavior (between Lambda =5 nm and Lambda =10 nm). (C) 2001 American Institute of Physics.

Direct observation of strong coupling in a dense plasma

We present differential x-ray scattering cross sections for a radiatively heated plasma showing overall consistency, in both form and absolute value, with theoretical simulations. In particular, the evolution of the plasma from a strongly coupled high density phase to a lower density weakly coupled phase is quite clearly shown in both experiment and simulation. The success of this experiment shows that x-ray scattering has the potential to become an extremely useful diagnostic technique for dense plasma physics.

Frequency coupling in dual frequency capacitively coupled radio-frequency plasmas

An industrial, confined, dual frequency, capacitively coupled, radio-frequency plasma etch reactor Exelan®, Lam Research has been modified for spatially resolved optical measurements. Space and phase resolved optical emission spectroscopy yields insight into the dynamics of the discharge. A strong coupling of the two frequencies is observed in the emission profiles. Consequently, the ionization dynamics, probed through excitation, is determined by both frequencies. The control of plasma density by the high frequency is, therefore, also influenced by the low frequency. Hence, separate control of plasma density and ion energy is rather complex.

Molecular Plasmonics with Tunable Exciton-Plasmon Coupling Strength in J-Aggregate Hybridized Au Nanorod Assemblies

Controlling coherent electromagnetic interactions in molecular systems is a problem of both fundamental interest and important applicative potential in the development of photonic and opto-electronic devices. The strength of these interactions determines both the absorption and emission properties of molecules coupled to nanostructures, effectively governing the optical properties of such a composite metamaterial. Here we report on the observation of strong coupling between a plasmon supported by an assembly of oriented gold nanorods (ANR) and a molecular exciton. We show that the coupling is easily engineered and is deterministic as both spatial and spectral overlap between the plasmonic structure and molecular aggregates are controlled. We think that these results in conjunction with the flexible geometry of the ANR are of potential significance to the development of plasmonic molecular devices.

Direct Observation of strong coupling in a laser-shock compressed plasma

In this Letter we report on a near collective x-ray scattering experiment on shock-compressed targets. A highly coupled Al plasma was generated and probed by spectrally resolving an x-ray source forward scattered by the sample. A significant reduction in the intensity of the elastic scatter was observed, which we attribute to the formation of an incipient long-range order. This speculation is confirmed by x-ray scattering calculations accounting for both electron degeneracy and strong coupling effects. Measurements from rear side visible diagnostics are consistent with the plasma parameters inferred from x-ray scattering data. These results give the experimental evidence of the strongly coupled ionic dynamics in dense plasmas.

The role of the relative voltage and phase for frequency coupling in a dual-frequency capacitively coupled plasma

Frequency coupling in multifrequency discharges is a complex nonlinear interaction of the different frequency components. An alpha-mode low pressure rf capacitively coupled plasma operated simultaneously with two frequencies is investigated and the coupling of the two frequencies is observed to greatly influence the excitation and ionization within the discharge. Through this, plasma production and sustainment are dictated by the corresponding electron dynamics and can be manipulated through the dual-frequency sheath. These mechanisms are influenced by the relative voltage and also the relative phase of the two frequencies.

Chain growth mechanism in Fischer-Tropsch synthesis: A DFT study of C-C coupling over Ru, Fe, Rh, and Re surfaces

A quantitative approach is used to understand the chain growth mechanism in FT synthesis on the Ru, Fe, Rh, and Re surfaces. The C-C coupling reactions are extensively calculated on the stepped metal surfaces. Combining the coupling barriers and reactant stabilities, we investigate the reaction rates of all possible C, + C-1 coupling pathways on the metal surfaces. It is found that (i) all the transition-state structures are similar on these surfaces, while some coupling barriers are very different; (ii) the dominant chain growth pathways on these surfaces are different: C + CH and CH + CH on Rh and Ru surfaces, C + CH3 on Fe surface, and C + CH on Re surface. The common features of the major coupling reactions together with those on the Co surface are also discussed.

Preparation of nanoparticulate metal catalysts in porous supports using an ionic liquid route; hydrogenation and C-C coupling

Aerogels containing palladium metal nanoparticles were prepared using an ionic liquid route and tested for activity towards hydrogenation and Heck C-C coupling reactions. (C) 2003 Elsevier B.V. All rights reserved.