Christopher Babayco, Pauline Chang, Donald P. Land, Richard A. Kiehl, and Atul N. Parikh, Langmuir 29, 8203-8207, 2013
This Letter describes Fourier-transform infrared spectroscopy evidence for the evolution of conformational order and coverage during the formation of n-alkanethiol monolayers on microdroplets of mercury from the solution phase. At the highest coverages obtained by self-assembly, the monolayer is characterized by predominantly all-trans conformational order. For partial monolayers obtained at arbitrarily quenched incubation periods, we find a continuous evolution of the chain conformational order with monolayer coverage. Analyzing these results in light of previously reported models from X-ray scattering reveals a complex self-assembly process in which the density-dependent evolution of the chain conformational order is coupled with that of molecular orientation and density.