Studies of double layer structure at gold electrodes using subtractively no
rmalized interfacial FTIR spectroscopy are presented. It is shown that, whe
n a hemispherical window is used to introduce the infrared radiation into t
he electrochemical cell, a significant increase in sensitivity results. Dat
a are presented illustrating the reorientation of solvent dipoles in the do
uble layer. In addition, results obtained for the accumulation of perchlora
te and nitrate ions at single crystal gold electrodes are discussed. In the
former case, analysis of the integrated intensity of the perchlorate band
at 1109 cm(-1) is used to show the potential region over which the surface
excess follows the Gouy-Chapman theory and the potential region in which pe
rchlorate ion is specifically adsorbed. (C) 1998 Published by Elsevier Scie
nce Ltd. All rights reserved.