Close‐Packed Two‐Dimensional Silver Nanoparticle Arrays: Quadrupolar and Dipolar Surface Plasmon Resonance Coupling

Silver nanoparticles (NPs) ranging in size from 40 to 100 nm were prepared in high yield by using an improved seed‐mediated method. The homogeneous Ag NPs were used as building blocks for 2D assembled Ag NP arrays by using an oil/water interface. A close‐packed 2D array of Ag NPs was fabricated by using packing molecules (3‐mercaptopropyltrimethoxysilane) to control the interparticle spacing. The homogeneous 2D Ag NP array exhibited a strong quadrupolar cooperative plasmon mode resonance and a dipolar red‐shift relative to individual Ag NPs suspended in solution. A well‐arranged 2D Ag NP array was embedded in polydimethylsiloxane film and, with biaxial stretching to control the interparticle distance, concomitant variations of the quadrupolar and dipolar couplings were observed. As the interparticle distance increased, the intensity of the quadrupolar cooperative plasmon mode resonance decreased and dipolar coupling completely disappeared. The local electric field of the 2D Ag NP array was calculated by using finite difference time domain simulation and qualitatively showed agreement with the experimental measurements.     

FORECASTING MINERAL SUPPLY FROM MINERAL RENT DATA

An optimal control model of exhaustible resources is used to clarify the long run relationship between mineral rent and depletion cost at the industry level. A standard first order condition of the time rate of change of rents is reformulated to reveal that rent data may be used to help forecast the rise in extraction costs resulting from resource depletion. This application of the theory of exhaustible resources is illustrated using historical mineral industry rent and extraction cost data. A forecast of U.S. coal extraction costs, following the method proposed in this paper, suggests that future rates of extraction cost increases will be similar to rates experienced in the past.     

Real-time recursive estimation of statistical parameters

Recursive algorithms for the computation of standard deviation and average deviation are derived and their applications in data acquisition are discussed. The relative speeds and accuracies of the two algorithms are compared for synthetic data. The performance of recursive estimation under shot and proportional noise limitations is also described. As an example of the utility of these algorithms, absorbance data with constant confidence intervals are collected regardless of incident and transmitted intensities. The desired precision is specified prior to data acquisition and used to control signal-averaging of the data in real time.     

Geometrical method for determining the surface damage threshold for femtosecond laser pulses

A new geometrical method to determine the surface damage threshold for ultrashort pulses is presented. It consists in the formation of a surface damage profile by a movement of the sample across the laser beam focus. A single measurement of the maximum transversal dimension of this damage profile, which depends solely on the laser beam power, is used to calculate the local damage threshold intensity. It is also theoretically shown that the damage in the transverse dimension can be controlled under the diffraction-limited spot.     

Hydrogen peroxide promoted hydroxylation of haloarenes and heteroarenes

Addition of aqueous hydrogen peroxide significantly accelerates the substitution reactions of hydroxide salts with haloarenes bearing electron withdrawing substituents. A similar effect is observed in the reactions of hydroxide salts with halogenated heteroarenes. Reactions are carried out in water or water-THF at ambient temperature or at 50-60 °C.     

Diffusion from sessile droplets through membranes

We analyze diffusion from a periodic array of hemispherical droplets through a membrane. We find that the multiple sources do not interact strongly, even when the droplets are closely spaced, so that the flux through the membrane appears nearly additive.     

A search technique for global optimization in a chaotic environment

We describe a new algorithm which uses the trajectories of a discrete dynamical system to sample the domain of an unconstrained objective function in search of global minima. The algorithm is unusually adept at avoiding nonoptimal local minima and successfully converging to a global minimum. Trajectories generated by the algorithm for objective functions with many local minima exhibit chaotic behavior, in the sense that they are extremely sensitive to changes in initial conditions and system parameters. In this context, chaos seems to have a beneficial effect: failure to converge to a global minimum from a given initial point can often be rectified by making arbitrarily small changes in the system parameters.     

Monte Carlo study of interfacial silicon suboxide layers and oxidation kinetics

A simple simulation scheme that simultaneously describes the growth kinetics of SiO₂ films at the nanometer scale and the SiO_x/Si interface dynamics (its extent, and spatial/temporal evolution) is presented. The simulation successfully applies to experimental data in the region above and below 10 nm, reproduces the Deal and Grove linear-parabolic law and the oxide growth rate enhancement in the very thin film regime (the so-called anomalous region). According to the simulation, the oxidation is governed mainly by two processes: (a) the formation of a transition suboxide layer and (b) its subsequent drift towards the silicon bulk. We found that it is the superposition of these two processes that produces the crossover from the anomalous oxidation region behavior to the linear-parabolic law.     

Metastability in the Potts model on the Cayley tree

Metastability in the ferromagneticp-state Potts model defined on the Cayley tree is discussed. It is shown that the sign of the boundary fieldH _s determines the order of the transition as well as the stability of the low-temperature phase. Lowering the temperature withH _s >0, a system withp<2 (p>2) will display a second (first)-order transition to a metastable (stable) phase. ForH _s >0 a second (first)-order transition to a metastable (stable) phase occurs ifp>2 (p<2). In this case the system also has a residual entropy which is negative forp<2.     

Vibrational dynamics of fullerene molecules adsorbed on metal surfaces studied with synchrotron infrared radiation

Infrared (IR) spectroscopy of chemisorbed C₆₀ on Ag (111), Au (110) and Cu (100) reveals that a non-IR-active mode becomes active upon adsorption, and that its frequency shifts proportionally with the charge transferred from the metal to the molecule by about 5 cm^-1 per electron. The temperature dependence of the frequency and the width of this IR feature have also been followed for C₆₀/Cu (100) and were found to agree well with a weak anharmonic coupling (dephasing) to a low-frequency mode, which we suggest to be the frustrated translational mode of the adsorbed molecules. Additionally, the adsorption is accompanied by a broadband reflectance change, which is interpreted as due to the scattering of conduction electrons of the metal surface by the adsorbate. The reflectance change allows determination of the friction coefficient of the C₆₀ molecules, which results in rather small values (∼2×10⁹ s^-1 for Ag and Au, and ∼1.6×10⁹ s^-1for Cu), consistent with a marked metallic character of the adsorbed molecules. Pre-dosing of alkali atoms onto the metal substrates drastically changes the IR spectra recorded during subsequent C₆₀ deposition: anti-absorption bands, as well as an increase of the broadband reflectance, occur and are interpreted as due to strong electron–phonon coupling with induced surface states. Received: 6 June 2001 / Accepted: 23 October 2001 / Published online: 3 April 2002