A study of the self-assembly of 1,4-benzenedimethanethiol (BDMT; HS-CH(2)-(C(6)H(4))-CH(2)-SH) monolayers on gold is presented. Self-assembled monolayers (SAMs) are characterized by reflection-absorption infrared spectroscopy (RAIRS), X-ray photoelectron spectroscopy (XPS), and spectroscopic ellipsometry (SE) measurements. The ensemble of measurements consistently shows that well-organized BDMT SAMs, with "standing-up" molecules, can be obtained on high quality gold films with incubation in n-hexane provided that N(2)-degassed solutions are used and all preparation steps are performed at 60 degrees C in the absence of ambient light. SE data indicate that the optical interface properties of the BDMT-Au system are different from those of simple alkanethiol SAMs. A possible mechanism for the formation of the "standing-up" phase from the lying-down phase via a hydrogen exchange reaction involving chemisorbed lying-down and free dithiol molecules is discussed.