Probing organization and structural characteristics of alkanethiols adsorbed on gold and of model alkane compounds through their valence electronic structure: An ultraviolet photoelectron spectroscopy study

In this paper we report an ultraviolet photoelectron spectroscopy (UPS) study of saturated alkane chains in various configurations and conformations. The dependence of the valence spectra on molecular structure characteristics has been assessed by comparing the results obtained from n-alkanethiol, alpha,omega-alkanedithiol, and alpha-cycloalkyl-omega-alkanethiol monolayers adsorbed on gold, and from gas-phase model alkane compounds. The differences between the spectra reflect directly the structural changes induced in the electronic structure of the alkane chains. We have determined the type of folding sequences adopted in a 1,12-dodecanedithiol monolayer. Angular dependent measurements and investigations on the photoelectron attenuation length have evidenced very fine structural differences between films obtained on deposited gold films, annealed gold films, and gold single crystals.