We investigate the feasibility of overlayer attenuated-total-reflectance (O-ATR) infrared spectroscopy as a surface analytical tool for studying reactions and molecular properties of adsorbates at surfaces exposed to aqueous nonelectrolyte solutions. Through modeling an O-ATR system by assuming it to comprise three, four, or n phases of homogeneous refractive index, one can use an electric-field analysis to determine how the parameters of adsorption free energy, overlayer thickness, initial angle of incidence, and internal-reflection element refractive-index influence solvent-subtracted O-ATR infrared-absorption spectra. The theory behind such an analysis is explained, and the results of its application are presented for hypothetical O-ATR systems consisting of either a zinc selenide or a germanium internal-reflection element, an iron or hematite overlayer, an adsorbate layer, and a solution of methylene chloride in water.
© 1998 Optical Society of America
Original Manuscript: July 23, 1997
Revised Manuscript: December 1, 1997
Published: June 1, 1998
John S. Loring and Donald P. Land, "Theoretical determination of parameters for optimum surface specificity in overlayer attenuated-total-reflection infrared spectroscopy," Appl. Opt. 37, 3515-3526 (1998)