Inelastic electron tunneling spectra and vibronic coupling density analysis of 2,5-dimercapto-1,3,4-thiadiazole and tetrathiafulvalene dithiol.

We calculate inelastic electron tunneling (IET) spectra for 2,5-dimercapto-1,3,4-thiadiazole (DMcT) and tetrathiafulvalene dithiol (TTF-DT) sandwiched between two gold electrodes using non-equilibrium Green's function (NEGF) theory. The calculated peak positions are in reasonable agreement with the experimental data. We also calculate IET spectrum for thiophene dithiol (Th-DT) sandwiched between two gold electrodes and compare it with that for the Au/DMcT/Au junction. Th-DT and DMcT can be distinguished using the IET spectroscopy by the peak of the C-C stretching mode. The peak intensity in the IET spectra is analyzed using vibronic coupling density (VCD) analysis. For the Au/DMcT/Au junction, large distribution of electron-density difference Δρ(HOMO) on the C-N bond is responsible for the intense peak of the C-N stretching mode; on the other hand, for Au/TTF-DT/Au junction, large distribution of Δρ(HOMO) on the central C=C bond is responsible for the intense peak of the C=C stretching modes.