Potential dependant infrared visible sum frequency generation spectroscopy (SFG) spectra of the aqueous/alkanethiol interface in the OH stretching region are presented. Spectra have been mathematically fit to extract information used to elucidate the structure and conformation of H2O at these electrochemical interfaces and the existence of a 'flip-flop' model for water in these environments is investigated. Comparison to recent work on Ag(111)/aqueous interface and other works on hydrophobic/aqueous interfaces corroborates assignments of OH bands in the 3800-2800 cm(-1) region. (C) 2007 Elsevier B.V. All rights reserved.