Sensitivity enhancement for evanescent-wave sensing using cavity-ring-down ellipsometry.

We demonstrate a method to increase the sensitivity of the s-p phase shift under total internal reflection (TIR) for optical sensing. This is achieved by the introduction of two simple dielectric layers to the TIR surface of a fused silica prism. The enhanced sensitivity is demonstrated using evanescent-wave cavity-ring-down-ellipsometry by measuring the refractive index of liquid mixtures and by studying the adsorption of polymers to the TIR surface of the fused silica prism.

Monitoring adsorption and sedimentation using evanescent-wave cavity ringdown ellipsometry.

We monitor the adsorption of Rhodamine 800, and the sedimentation of a polytetrafluoroethylene (PTFE) suspension at the surface of a fused-silica prism, by measuring both the absorption and s-p phase shift Δ of a 740 nm probe laser beam, using evanescent-wave cavity ringdown ellipsometry (EW-CRDE). The two systems demonstrate the complementary strengths of EW-CRDE, as the progress of adsorption of the Rhodamine 800 dye can only be observed sensitively via the measurement of absorption, whereas the progress of sedimentation of PTFE can only be observed sensitively via the measurement of Δ. We show that EW-CRDE provides a sensitive method for the measurement of Δ and demonstrates precision in Δ of about 10(-4) deg.

Evanescent-Wave Cavity Ring-Down Ellipsometry.

We introduce the new technique of evanescent-wave cavity ring-down ellipsometry (EW-CRDE), used for the measurement of ellipsometric angles of samples at a solid-gas or solid-liquid interface, and achieve phase-shift measurements with precision of ∼0.01°. We demonstrate the technique by measuring the time-dependent refractive index of methanol-water mixtures and thin films at the liquid/fused-silica interface, showing that the monitoring of monolayers on microsecond time scales using EW-CRDE should be achievable.

(2+1) laser-induced fluorescence of spin-polarized hydrogen atoms.

We report the measurement of the spin polarization of hydrogen (SPH) atoms by (2+1) laser-induced fluorescence, produced via the photodissociation of thermal HBr molecules with circularly polarized 193 nm light. This scheme, which involves two-photon laser excitation at 205 nm and fluorescence at 656 nm, offers an experimentally simpler polarization-detection method than the previously reported vacuum ultraviolet detection scheme, allowing the detection of SPH atoms to be performed more straightforwardly, from the photodissociation of a wide range of molecules and from a variety of collision experiments.

Discrete sums for the rapid determination of exponential decay constants.

Several computational methods are presented for the rapid extraction of decay time constants from discrete exponential data. Two methods are found to be comparably fast and highly accurate. They are corrected successive integration and a method involving the Fourier transform (FT) of the data and the application of an expression that does not assume continuous data. FT methods in the literature are found to introduce significant systematic error owing to the assumption that data are continuous. Corrected successive integration methods in the literature are correct, but we offer a more direct way of applying them which we call linear regression of the sum. We recommend the use of the latter over FT-based methods, as the FT methods are more affected by noise in the original data.

Hemoglobin adsorption to silica monitored with polarization-dependent evanescent-wave cavity ring-down spectroscopy.

Evanescent-wave cavity ring-down spectroscopy was used to monitor the adsorption of human hemoglobin to a fused-silica surface from aqueous solution. An uncoated dove prism was situated in a ring-down cavity such that the beam entered and exited with a normal-incidence geometry. This afforded ring-down times as high as 5 mus and values of sigma(tau)/tau as low as 0.3%. Normal-incidence geometry permits the detection of both S- and P-polarized light, yielding some information of the orientation of adsorbates. The orientation of the adsorbed hemoglobin molecules is found to change as adsorption progresses, but with a different time profile than adsorption itself. The adsorption kinetics from a quiescent solution is consistent with a reaction-diffusion model that includes both reversible and irreversible adsorption operating in parallel. Systems behaving according to this model also seem to display adsorption isotherms, although the increased adsorption from more concentrated solutions is only a consequence of the system being under kinetic control. In some cases, this may be sufficient to explain the paradox of protein adsorption systems which seem to be both irreversible and consistent with isotherm models as well.