Search

Transient pump–probe measurements have been made on betaine-30, the solvent polarity probe. Betaine-30 is composed of organic donor and acceptor groups, D+A-⇄kethνDA (excited state). The transient data has been analyzed to measure ket, the electron transfer (et) rate constant, in polar solvents for this inverted regime et. The observed rate constant ket,obs in various polar solvents is as much as a factor of 108 larger than is predicted by the standard, classical, implementation of the theory of Sumi and Marcus, using Kjaer and Ulstrup’s estimates for necessary parameters. In contrast, a quantum treatment of the vibrational modes by Jortner and Bixon, which includes the dynamic solvent effect, predicts that the rate should be approximately ket,JB[bar_over_tilde:_approx._equal_to]1/〈τs>. This is close to the experimental results ([bar_over_tilde:_approx._equal_to]1012 s-1) in typical polar aprotic solvents. However, in highly viscous, slowly relaxing solvents, ket,JB≪ket,obs. This is taken as evidence that the efficient coupling modes for the et in these environments is not the ‘‘conventional solvent coordinate.’’ It is shown that a hybrid of the Jortner/Bixon and Sumi/Marcus theories can physically account for the results. The kinetic behavior of betaine-30 in slowly relaxing solvents is shown to be in the ‘‘diffusionless limit’’ of the hybrid, generalized Sumi–Marcus/Jortner–Bixon picture. [ABSTRACT FROM AUTHOR]

The inverted regime photoinduced electron transfer kinetics of betaine-30 have been investigated over a broad temperature range, revealing very little temperature dependence. For example, for betaine-30 in a polystyrene film, the electron transfer rate constant, kET, changes by less than a factor of 3 from T=293 K to T=34 K. The results are in striking contrast to predictions of contemporary electron transfer theories which employ classical nuclear modes to accept some or all of the energy of the electron transfer event. The comparison of theory and experiment for the betaines demonstrates that a full quantum mechanical theory is necessary to accurately describe the electron transfer kinetics of the betaines in environments with slow dielectric relaxation. The conclusions drawn for the betaines may also apply to other molecular examples of inverted regime electron transfer in slowly relaxing environments. [ABSTRACT FROM AUTHOR]

Scattering type scanning near-field optical microscopy (s-SNOM) allows sub diffraction limited spatial resolution. Interferometric homodyne detection in s-SNOM can amplify the signal and extract vibrational responses based on sample absorption. A stable reference phase is required for a high quality homodyne-detected near-field signal. This work presents the development of a phase stabilization mechanism for s-SNOM to provide stable homodyne conditions. The phase stability is found to be better than 0.05 rad for the mid infrared light source. Phase stabilization results in improved near field images and vibrational spectroscopies. Spatial inhomogeneities of the boron nitride nanotubes are measured and compared. [ABSTRACT FROM AUTHOR]

An interferometric method is used to enhance the weak scattered signal in apertureless near-field scanning infrared microscopy. The method involves introducing a homodyning reference field, and amplifies the desired signal field by the magnitude of the reference field. This method markedly improves the signal-to-noise ratio of the detected signal, over the nonhomodyned experiment. A model for the dependence of the near-field signal, as a function of the normal distance of the tip from the surface, is discussed. Application of a model in which the tip is represented by two spherical scatterers, one large and one small, indicates the electromagnetic field enhancement is 90-fold greater at the sharp apex of the metallic probe tip. [ABSTRACT FROM AUTHOR]

Presents a study that constructed and combined solid state Ti:sapphire lasers with nonlinear optics to produce a resolution absorption spectrometer with specific tunability and sensitivity levels. Tunable light generation and array detection technology; Suitability of different infrared nonlinear optical materials.

This work systematically evaluates the effect of array periodicity on the near infrared transmission characteristics of annular aperture arrays (AAAs) in gold films. Both the experimental and theoretical transmission spectra of AAAs are shown to be sensitive to the period and the arrangement of the apertures within the array. The spectra of square arrays with periods ranging from 1400 to 600 nm show a strong correlation with surface plasmon polariton (SPP)-Bloch modes of the metal/dielectric interfaces. For rectangular AAAs the transmission spectra are significantly attenuated and reveal a polarization sensitivity that arises from the breaking of the symmetry and degeneracy of the SPP-Bloch modes. [ABSTRACT FROM AUTHOR]