Raman signal intensities from the 997 cm−1 ring breathing mode of thiophenol monolayers adsorbed at Ag, Au, and Pt surfaces were employed for determination of absolute surface enhancement factors (SEFs). Unlike previous estimations of SEFs, these SEFs are determined by referencing the surface-enhanced Raman scattering (SERS) intensities to the unenhanced Raman scattering at Pt surfaces. The surfaces studied include those commonly prepared in a laboratory ambient and those prepared in vacuum. Surfaces prepared in ambient include polycrystalline Ag electrochemically roughened by an oxidation-reduction cycle (ORC), mechanically polished (MP) polycrystalline Ag, chemically polished (CP) polycrystalline Ag, Ag (111), MP polycrystalline Au, and MP polycrystalline Pt. Vacuum environment surfaces include coldly deposited Ag films (cold Ag) and room temperature-deposited (RT) “thick” Ag films. Each of these thiophenol/metal systems was sampled with an excitation wavelength (λex) of 514.5 nm; MP Au surfaces were also studied with λex of 720 nm. SEFs of 2.0 × 104 for ORC Ag, 5.3 × 103 for MP Ag, 160 for cold Ag, 64 for MP Au720 (λex = 720 nm), 69 for Ag (111), 39 for CP Ag, 7.9 for RT “thick” Ag, and 2.2 for MP Au514.5 (λex 514.5 nm) are observed relative to the SEF of MP Pt, which is assigned as 1. For practical purposes, the significance of the magnitudes of these SEFs is discussed in terms of estimated surface Raman limits of detection (LODs).

Dry reverse micelles of the anionic twin-tailed surfactant bis(2-ethylhexyl) sulfosuccinate (AOT) dissolved in nonpolar solvents spontaneously form an organogel when p-chlorophenol is added in a 1:1 AOT:phenol molar ratio. The solvents used were benzene, toluene, m-xylene, 2,2,4-trimethylpentane (isooctane), decane, dodecane, tetradecane, hexadecane, and 2,6,10,14-tetramethylpentadecane (TMPD). The proposed microstructure of the gel is based on strands of stacked phenols linked to AOT through hydrogen bonding. Small-angle X-ray scattering (SAXS) spectra of the organogels suggest a characteristic length scale for these phenol-AOT strands that is independent of concentration but dependent on the chemical nature of the nonpolar solvent used. Correlation lengths determined from the SAXS spectra indicate that the strands self-assemble into fibers. Direct visualization of the gel in its native state is accomplished by using tapping mode atomic force microscopy (AFM). It is shown that these organogels consist of fiber bundle assemblies. The SAXS and AFM data reinforce the theory of a molecular architecture consisting of three length scales-AOT/phenolic strands (ca. 2 nm in diameter) that self-assemble into fibers (ca. 10 nm in diameter), which then aggregate into fiber bundles (ca. 20-100 nm in diameter) and form the organogel.

The quantity and chemical nature of carbonaceous impurities remaining on polycrystalline Ag surfaces after preparation depend on the protocol used for cleaning. The effectiveness of several preparation protocols was investigated in this study: mechanical polishing with successively finer grades of alumina, Ar + sputtering, chemical polishing, and chemical polishing followed by Tl underpotential deposition. The impurities detected on polycrystalline Ag surfaces subjected to these preparation procedures are carbon, oxygen, and aluminum, and these are qualitatively and quantitatively identified with X-ray photoelectron spectroscopy. With Raman spectroscopy, these carbonaceous impurities are qualitatively identified as graphite, hydrocarbon, and cyanide species, the last of these being present only on the chemically polished surfaces.

Approaches for frequency/wavelength calibration of multichannel Raman spectrometers are presented. These approaches are directed towards practical use in laboratories in which multipurpose or specialized applications result in the need for frequent spectrometer calibration. These approaches are also useful when the sample type or configuration does not permit calibration by more routine methods. Guidelines are presented for effective use of polynomials commonly found in spectrometer calibration software for conversion of pixel number to either wavenumber or wavelength. Guidelines for the selection and use of Raman calibration standards are also presented. Standards currently used for calibration of Raman spectrometers are reviewed. Improved frequency data for indent' and the Ar+ plasma lines are presented, along with frequency data for two materials (imidazole and α-cyclodextrin) which are recommended for use as solid Raman standards.