Stable silver thin films were prepared either by chemical deposition or by argon sputtering on germanium and silicon substrates, respectively, and used as electrodes for in situ infrared spectroscopy experiments with a Kretschmann internal reflection configuration. The spectra obtained for acetate anions adsorbed from neutral solutions showed a noticeable intensity enhancement (SEIRA effect). This enhanced absorption has been related to the surface structure of the films that have been characterized by ex situ STM and in situ electrochemical measurements (lead underpotential deposition, UPD). STM images of the chemically deposited silver films show mean grain sizes ranging from ca. 20 to 90 nm for deposition times between 2 and 20 min, and the absence of flat domains. On the other hand, STM images of the films deposited by argon sputtering show mean grain sizes around 30 nm for a film growth rate of 0.05 nm s(-1) and 70 nm for a film growth rate of 0.005 nm s(-1). In this latter case, atomically flat domains up to 50 nm wide have been observed. This observation is consistent with a more defined voltammetric profile for lead UPD, that indicates a higher degree of surface order. Moreover, the roughness factor obtained from the charge density involved in lead UPD in the case of the sputtered silver film is lower than that measured for the chemically deposited silver film. All these structural data can be connected with the observations on the effect of deposition conditions of the silver film on the SEIRA effect for adsorbed acetate. Maximum enhancement is observed for chemically deposited films and sputtered films at high deposition rate for which the grain size is around 40-60 nm. The increase of the grain size for the sputtered silver films deposited at decreasing deposition rates can be related to the observed decrease in the SEIRA effect. (c) 2007 Elsevier Ltd. All rights reserved.