This paper describes the optical analysis, construction, testing, and application of a cell for measuring <i>in situ</i> IR reflection spectra in the C-H stretching region of monolayer films of long-chain alkanethiolates on evaporated Au films beneath a thin overlayer (∼1 μm) of aqueous solution. The cell facilitates the interchange of sample (monolayer-coated) and reference substrates—a major improvement over previous designs. This allows the acquisition of an IR reflection spectrum of a monolayer without the application of electrochemical or polarization-modulation methods. The optical properties of the cell are analyzed within the context of classical electromagnetic theory; the effects of angle of incidence, solution layer thickness, and solution composition (H<sub>2</sub>O and D<sub>2</sub>,O) and the refractive indices of the IR-transparent window material on the observed spectrum are specifically examined. Calculations of both the mean-square electric fields and the reflection spectra for a monolayer of octadecanethiolate on Au are presented. From these results, conditions to achieve high surface detectability are identified, and optically induced alterations in the intensities and shapes of the monolayer spectrum are delineated. Spectra for the same monolayer are measured to test these predictions as well as to assess the practical limitations of the experimental technique.

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