First-Principles Study for Detection of Inelastic Electron Transport in Molecular Junctions by Internal Substitution

The idea of doping and chemical substitutions for bridge molecules is one of promising techniques to control the transport properties and engineering of molecular devices. In the present article, we extend this concept and propose the use of internal substitutions to detect the mechanism of ballistic and inelastic transport through molecular junctions. By performing first-principles transport calculations for several internally substituted systems, we show systematic pathway analysis of tunneling electrons and vibronic states as well as electron−phonon couplings on bridge molecules. The correlation of inelastic electron tunneling spectroscopy (IETS) and Raman spectroscopy is also discussed.