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Optical constants (3000–8000 Å) and layer thicknesses of TiO2/Ag/TiO2 optical coatings are determined using variable angle of incidence spectroscopic ellipsometry. Ellipsometrically determined silver layer thicknesses agree well with those obtained by cross-sectional transmission electron microscopy. Also, spectral characteristics, absent in bulk silver data, are observed in n and k spectra for the thin silver layers. It is suggested that these structures may be caused by plasmon effects from the silver layers.