Waiting time between charging and discharging processes in molecular junctions

When electric current flows through a molecular junction, the molecule constantly charges and discharges by tunneling electrons. These charging and discharging events occur at specific but random times and are separated by stochastic time intervals. These time intervals can be associated with the dwelling time for a charge (electron or hole) to reside on the molecule. In this paper, the statistical properties of these time intervals are studied and a general formula for their distribution is derived. The theory is based on the Markovian master equation which takes into account transitions between the vibrational states of charged and neutral molecules in the junction. Two quantum jump operators are identified from the Liouvillian of the master equation-one corresponds to charging of the molecule and the other discharges the molecule back to the neutral state. The quantum jump operators define the conditional probability that given that the molecule was charged by a tunneling electron at time t, the molecule becomes neutral at a later time t + τ discharging the electron to the drain electrode. Statistical properties of these time intervals τ are studied with the use of this distribution.