Total-internal-reflection broad-bandwidth sum frequency generation spectroscopy of hexadecanethiol adsorbed on thin gold film deposited on CaF2.

Sum frequency vibrational spectra for hexadecanethiol (HDT) adsorbed on thin gold film deposited on the surface of a CaF2 prism have been measured using total-internal reflection broad-bandwidth sum frequency generation (TIR-BBSFG) spectroscopy. The bands attributed to the CH3 symmetric and asymmetric stretching vibrational modes were observed in the sum frequency vibrational spectra. The orientation of the methyl groups was analyzed using the ratio of the intensities of the two modes. The methyl groups of HDT on the thin gold film were much more randomly orientated than those on Au( 111).