Optical field control of charge transmission through a molecular wire. I. Generalized master equation description

A generalized master equation description of charge transmission through a single molecule that goes beyond a perturbative treatment of electron-vibrational coupling and accounts for nonequilibrium vibrational distributions is presented. By utilizing a projection superoperator formalism, exact expressions for the generalized master equation kernels that include intramolecular vibrational energy redistribution, excited electronic levels, as well as their optical excitation and de-excitation are derived. This enables one to study optical current switching in the case of weak electron-lead coupling and large reorganization energy upon charging. Additionally, it is possible to quantify the influence of intramolecular vibrational energy redistribution and excited state de-excitation on the current switching.