Image charge dynamics in time-dependent quantum transport

Abstract

In this work, we investigate the effects of the electron-electron interaction between a molecular junction and the metallic leads in time-dependent quantum transport. We employ the recently developed embedded Kadanoff-Baym method [Phys. Rev. B 80, 115107 (2009)] and show that the molecule-lead interaction changes substantially the transient and steady-state transport properties. We first show that the mean-field Hartree-Fock (HF) approximation does not capture the polarization effects responsible for the renormalization of the molecular levels neither in nor out of equilibrium. Furthermore, due to the time-local nature of the HF self-energy, there exists a region in parameter space for which the system does not relax after the switch-on of a bias voltage. These and other artifacts of the HF approximation disappear when including correlations at the second-Born or GW levels. Both these approximations contain polarization diagrams, which correctly account for the screening of the charged molecule. We find that by changing the molecule-lead interaction, the ratio between the screening and relaxation time changes, an effect which must be properly taken into account in any realistic time-dependent simulation. Another important finding is that while in equilibrium the molecule-lead interaction is responsible for a reduction of the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap and for a substantial redistribution of the spectral weight between the main spectral peaks and the induced satellite spectrum, in the biased system it can have the opposite effect, i.e., it sharpens the spectral peaks and opens the HOMO-LUMO gap.