Raman scattering and fluorescence emission in a single nanoaperture: Optimizing the local intensity enhancement

We investigate the potential of a single subwavelength aperture milled in an aluminium film to enhance the local electromagnetic field. We compare the Raman scattering of unadsorbed chlorobenzene molecules and the fluorescence emission of Cyanine-5 dyes, having the same excitation and collection setup for both experiments. For the optimal nanoaperture diameter, we report a clear enhancement factor of about 5 of the Raman scattering intensity per unit volume. Since Raman scattering probes the molecular vibrational levels and avoids the resonant pumping of a real excited state, the observed Raman enhancement is disconnected from the effects of the molecular energy levels alteration previously reported for fluorescent dyes. The observations are similar for both Raman and fluorescence experiments, and stand in good agreement with numerical electromagnetic computations of the excitation intensity inside the nanoaperture.     

An easily accessible cisoid isoprenoid synthon

Five-step preparation of the cisoid isoprenoid synthon $\text{5}$ and its use for the two-step C₅-homologation is described.     

Asymptotics of determinants of 4-th order operators at zero

We consider fourth order ordinary differential operators on the half-line and on the line, where the perturbation has compactly supported coefficients. The Fredholm determinant for this operator is an analytic function in the whole complex plane without zero. We describe the determinant at zero. We show that in the generic case it has a pole of order 4 in the case of the line and of order 1 in the case of the half-line.     

Vibrations of a continuous web on elastic supports

We consider an infinite, homogenous linearly elastic beam resting on a system of linearly elastic supports, as an idealized model for a paper web in the middle of a cylinder-based dryer section. We obtain closed-form analytical expressions for the eigenfrequencies and the eigenmodes. The frequencies increase as the support rigidity is increased. Each frequency is bounded from above by the solution with absolutely rigid supports, and from below by the solution in the limit of vanishing support rigidity. Thus in a real system, the natural frequencies will be lower than predicted by commonly used models with rigid supports.     

Complete thermodynamically consistent kinetic model of particle nucleation and growth: numerical study of the applicability of the classical theory of homogeneous nucleation

A complete thermodynamically consistent elementary reaction kinetic model of particle nucleation and growth from supersaturated vapor was developed and numerically evaluated to determine the conditions for the steady-state regime. The model treats all processes recognized in the aerosol science (such as nucleation, condensation, evaporation, agglomerationcoagulation, etc.) as reversible elementary reactions. It includes all possible forward reactions (i.e., of monomers, dimers, trimers, etc.) together with the thermodynamically consistent reverse processes. The model is built based on the Kelvin approximation, and has two dimensionless parameters: S0-the initial supersaturation and Theta-the dimensionless surface tension. The time evolution of the size distribution function was obtained over the ranges of parameters S0 and Theta. At low initial supersaturations, S0, the steady state is established after a delay, and the steady-state distribution function corresponds to the predictions of the classical nucleation theory. At high initial supersaturations, the depletion of monomers due to condensation on large clusters starts before the establishing of the steady state. The steady state is never reached, and the classical nucleation theory is not applicable. The boundary that separates these two regimes in the two dimensionless parameter space, S0 and Theta, was determined. The model was applied to several experiments on water nucleation in an expansion chamber [J. Wolk and R. Strey, J. Phys. Chem. B 105, 11683 (2001)] and in Laval nozzle [Y. J. Kim et al., J. Phys. Chem. A 108, 4365 (2004)]. The conditions of the experiments performed using Laval nozzle (S0=40-120) were found to be close to the boundary of the non-steady-state regime. Additional calculations have shown that in the non-steady-state regime the nucleation rate is sensitive to the rate constants of the initial steps of the nucleation process, such as the monomer-monomer, monomer-dimer, etc., reactions. This conclusion is particularly important for nucleation from supersaturated water vapor, since these processes for water molecules at and below the atmospheric pressure are in the low pressure limit, and the rate constants can be several orders of magnitude lower than the gas kinetic. In addition, the impact of the thermodynamic inconsistency of the previously developed partially reversible kinetic numerical models was assessed. At typical experimental conditions for water nucleation, S0=10 and Theta=10 (T=250 K), the error in the particle nucleation rate introduced by the thermodynamic inconsistency exceeds one order of magnitude.     

Asymptotics of the S-matrix for perturbed Hill operators

We consider the Schrödinger operator with a periodic potential p plus a compactly supported potential q on the real line. We assume that both p and q have m ? 0 derivatives. For generic p, the essential spectrum of the operator has an infinite sequence of open gaps. We determine the asymptotics of the S-matrix at high energy.     

Fluorescence modulation of eosin Y in a PMMA film by diarylethene switching

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The estimates of periodic potentials in terms of effective masses

LetG _n=(A _n ⁻ , A _n ⁺ ),n≧1, denote the gaps,M _n ^± be the effective masses and Σn=[A _n−1 ⁺ ,A _n ^- ],A ₀ ⁺ =0, be the spectral bands of the Hill operatorT=−d ²/dx ²+V(x) inL ² (R), whereV is a 1-periodic real potential fromL ²(0,1). Let the length gapL _n=|G_n|, h_n be the height of the corresponding slit on the quasimomentum domain and Δ_n=π²(2n−1)−∣Σ_n∣>0 be the band reduction. Let ,n≧1, denote the gap length for the operator . Introduce the sequencesL={L_n}, h={h_n}, l={l_n}, Δ={Δ_n},M ^±={M _n ^± } and the norms ,m≧0. The following results are obtained: i) The estimates of‖V‖, ‖L‖, ‖h‖ ₁, ‖l‖₁, ‖δ‖ in terms of ‖M^±‖₂, ii) identities for the Dirichlet integral of quasimomentum and integral of potentials and so on, iii) the generation of i), ii) for more general potentials. The research described in this publication was made possible in part by grant from the Russian Fund of Fundamental Research and INTAS.     

Monte Carlo simulations of critical cluster sizes and nucleation rates of water

We have calculated the critical cluster sizes and homogeneous nucleation rates of water at temperatures and vapor densities corresponding to experiments by Wolk and Strey [J. Phys. Chem B 105, 11683 (2001)]. The calculations have been done with an expanded version of a Monte Carlo method originally developed by Vehkamaki and Ford [J. Chem. Phys. 112, 4193 (2000)]. Their method calculates the statistical growth and decay probabilities of molecular clusters. We have derived a connection between these probabilities and kinetic condensation and evaporation rates, and introduce a new way for the calculation of the work of formation of clusters. Three different interaction potential models of water have been used in the simulations. These include the unpolarizable SPC/E [J. Phys. Chem. 91, 6269 (1987)] and TIP4P [J. Chem. Phys. 79, 926 (1983)] models and a polarizable model by Guillot and Guissani [J. Chem. Phys. 114, 6720 (2001)]. We show that TIP4P produces critical cluster sizes and a temperature and vapor density dependence for the nucleation rate that agree well with the experimental data, although the magnitude of nucleation rate is constantly overestimated by a factor of 2 x 10(4). Guissani and Guillot's model is somewhat less successful, but both the TIP4P and Guillot and Guissani models are able to reproduce a much better experimental temperature dependency of the nucleation rate than the classical nucleation theory. Using SPC/E results in dramatically too small critical clusters and high nucleation rates. The water models give different average binding energies for clusters. We show that stronger binding between cluster molecules suppresses the decay probability of a cluster, while the growth probability is not affected. This explains the differences in results from different water models.