Theory of inelastic tunneling spectroscopy of a single molecule – Competition between elastic and inelastic current

A theory of inelastic electron tunneling spectroscopy of a single molecule with scanning tunneling microscope is presented using the Keldysh Green’s function method for an adsorbate-induced resonance coupled to the molecular vibration. It is found that the correction to the tunneling current is expressed in terms of the transmission probability; the correction is negative for the elastic part of the current and positive for the inelastic one. The differential conductance (dI/dV) exhibits an increase or decrease at the threshold corresponding to the opening of inelastic channel depending on the sign of the correction, and the size of this conductance jump is scaled with the vibrational damping due to electron–hole pair excitation. The lineshape of d2I/dV2-spectra calculated using a renormalized adsorbate Green’s function evolves from an antisymmetric dip to a peak through the derivative-like one as the position of the adsorbate resonance recedes from the Fermi level of the substrate.